METHOD OF MAKING A BRANCHED POLYMER, A BRANCHED POLYMER AND USES OF SUCH A POLYMER

Abstract

A method of making a branched polymer comprising (CC)(CC)CO groups is provided. The method comprises: (i) Providing, in admixture, at least one monofunctional monomer comprising one polymerisable carbon-carbon double bond per monomer, at least one multifunctional monomer comprising at least two polymerisable carbon-carbon double bonds per monomer, at least one chain transfer agent comprising a carbonyl group; (ii) Forming a polymer from the mixture; and (iii) Hydrolysing the polymer. A branched polymer is further provided.

Claims

1. A method of making a branched polymer comprising (CC)(CC)CO groups, the method comprising: (i) Providing, in admixture, at least one monofunctional monomer comprising one polymerisable carbon-carbon double bond per monomer, at least one multifunctional monomer comprising at least two polymerisable carbon-carbon double bonds per monomer, at least one chain transfer agent comprising an aldehyde or a ketone, and optionally at least one polymerisation initiator; and (ii) Forming a polymer from the mixture; (iii) Hydrolysing the polymer thereby forming a hydrolysed polymer.

2. (canceled)

3. A method according to claim 1 wherein the amount of chain transfer agent comprising an aldehyde or ketone is at least 5 mol % and no more than 50 mol % of the amount of monofunctional monomer.

4. (canceled)

5. A method according to claim 1 wherein the ratio of the number of moles of the chain transfer agent comprising an aldehyde or ketone to the number of moles of multifunctional monomer is at least 10:1 and no more than 300:1.

6. (canceled)

7. A method according to claim 1 wherein substantially all of the chain transfer agent comprising an aldehyde or ketone is admixed with one or more of at least one monofunctional monomer, at least one multifunctional monomer and optionally at least one polymerisation initiator (if present) at the start of the polymerisation reaction.

8. A method according to any of claims 1 to 6 wherein the method comprises delaying addition of at least some of the chain transfer agent comprising an aldehyde or ketone.

9-10. (canceled)

11. A method according to claim 8 wherein substantially no chain transfer agent comprising an aldehyde or ketone is added to the reaction mixture at the commencement of the polymerisation reaction.

12. A method according to claim 8 comprising adding at least 50% of said chain transfer agent before the conversion % of the monofunctional monomer reaches 60%.

13. A method according to claim 8 comprising providing at least a portion of the chain transfer agent comprising an aldehyde or ketone in admixture with one or more of at least one monofunctional monomer, at least one multifunctional monomer and optionally at least one polymerisation initiator (if present) before the start of the polymerisation reaction.

14. (canceled)

15. A method according to claim 1 comprising providing more than one monofunctional monomer, each monofunctional monomer comprising one (and only one) polymerisable carbon-carbon double bond.

16. (canceled)

17. A method according to claim 1 wherein the amount of multifunctional monomer is at least 0.05 mol % and no more than 2 mol % of the monofunctional monomer content.

18. (canceled)

19. A method according to any preceding claim 1 comprising: (i) a solution polymerisation, either as a single solvent, or the solvents used in the solution polymerisation comprise a mixture of a first solvent component having a first chain transfer constant and a second solvent component having a second chain transfer constant, the second chain transfer constant being at least five times greater than the first chain transfer constant, or (ii) a suspension polymerisation.

20-21. (canceled)

22. A method according to claim 1 wherein the polymer is hydrolysed to form a hydrolysed polymer having a degree of hydrolysis of at least 60 mol %.

23. A method according to claim 1 wherein the polymer has a UV absorbance at 280 nm which is at least three times that at 320 nm.

24. A branched polymer makeable in accordance with the method of claim 1.

25. A branched polymer comprising (CC)(CC)CO moieties located at chain ends, with a UV absorbance value at 280 nm which is at least three times that at 320 nm, the polymer comprising residues of: (i) At least one monofunctional monomer having one polymerisable double bond per molecule; (ii) At least one multifunctional monomer having at least two polymerisable double bonds per molecule; and (iii) At least one chain transfer agent comprising an aldehyde or ketone.

26. (canceled)

27. A polymer according to claim 25 comprising 0.5 mol % and no more than 45 mol % chain transfer agent comprising an aldehyde or ketone, based on the number of moles of residues of monofunctional monomer.

28. (canceled)

29. A polymer according to claim 25 comprising ester and hydroxyl groups and optionally carboxylic acid groups and having a degree of hydrolysis of at least 60 mol %.

30-31. (canceled)

32. A polymer according to claim 25 having a dispersity (defined as M.sub.w/M.sub.n) of at least 3 and no more than 200.

33-34. (canceled)

35. A polymer according to claim 25 wherein the intensity of the UV adsorption peak at 280 nm generated by a solution of the polymer is at least four times the intensity of the UV absorption peak at 320 nm.

36. A polymer according to claim 25 wherein the polymer contains (conjugated) carboxylic acid groups derived from a substituted, or an unsubstituted monofunctional monomer.

37. Use of the polymer in accordance with claim 25 in a suspension polymerisation of an unsaturated monomer wherein the polymer is used as a primary suspending agent.

38. A suspension polymerisation reaction composition comprising a continuous phase in which is dispersed liquid beads of monomer to be polymerised, and the polymer of claim 25.

Description

DETAILED DESCRIPTION

[0099] In the description below, the following abbreviations or terms are used:

[0100] IPAisopropyl alcohol (2-propanol)

[0101] TTT1,3,5-triallyl-1,3,5-triazine-2,4,6-trione

[0102] M.sub.nnumber average molecular weight

[0103] M.sub.Wweight average molecular weight

[0104] PDIM.sub.W/M.sub.n

[0105] KK-value

[0106] RAResidual acetate (%(w/w))

[0107] DHDegree of hydrolysis (mol %)

[0108] MeOHmethanol

[0109] VAcvinyl acetate

[0110] AIBNazobisisobutyronitrile

[0111] AIVNazobis(2-methylbutyronitrile)

[0112] .sup.tBP2EHt-butyl peroxy-2-Ethylhexanoate

[0113] CTAchain transfer agent

[0114] 4-L/SP4 litre volume reactor

[0115] 1-L/SP1 litre volume reactor

[0116] UV.sub.280intensity of the UV adsorption peak at 280 nm expressed at 1% (w/w) concentration

[0117] UV.sub.320intensity of the UV adsorption peak at 320 nm expressed at 1% (w/w) concentration

[0118] DHdegree of hydrolysis (mol %)the degree of hydrolysis is calculated from the Residual acetate (RA) value. The Residual acetate value for the polymer is measured by refluxing with a known excess of 0.1N sodium hydroxide solution. A blank determination with no polymer is also carried out. The remaining sodium hydroxide is titrated against 0.1N hydrochloric acid using phenol phthalein indicator. The residual acetate in the polymer is calculated using the formula below.

[00001]$.Math.\mathrm{Residual}.Math..Math.\mathrm{Acetate}\left(\%.Math.\left(w/w\right)\right)=\frac{\left(V_{\mathrm{blank}}-V_{\mathrm{Titre}}\right)0.86}{\mathrm{Weight}.Math..Math.\mathrm{of}.Math..Math.\mathrm{sample}}$$\mathrm{Degree}.Math..Math.\mathrm{of}.Math..Math.\mathrm{hydrolysis}\left(\mathrm{mol}.Math..Math.\%\right)=100\frac{1.9545.Math.\left(100-\mathrm{RA}\right)}{\left[1.9545.Math.\left(100-\mathrm{RA}\right)\right]-\mathrm{RA}}$

[0119] 4% (w/w) viscositythe viscosity of a 4% (w/w) solution of a poly(vinyl alcohol)-co-poly(vinyl acetate) was measured as described above.

[0120] TSCTotal solid content. The percentage total solids content (TSC) is determined by weighing a sample of material before and after drying in a vacuum oven, at about 900 to 1000 mbar and 105 C., for one hour.

[0121] MHMark-Houwink constant

[0122] This was generated by the SEC software, data collection was using Cirrus Multi Online GPC/SEC Version 3.2 supplied by Varian Inc. The data analysis was made using Cirrus Multi Offline GPC/SEC Version 3.2 supplied by Varian Inc.

[0123] The Mark-Houwink equation is used to describe the relationship between the intrinsic viscosity of a polymer and its relative molecular mass:

[]=K.Math.M.sub.r.sup.a

[0124] Where

[0125] []=intrinsic viscosity, and K and a are constants (often called Mark-Houwink constants) which depend upon the nature of the polymer and the solvent, as well as on temperature and is usually one of the relative molecular mass averages (http://goldbook.iupac.org/M03706.html). For a given polymer (and equivalent degree of hydrolysis) in the same solvent at the same temperature and concentration, K will be constant and only the exponential term a will reflect the linear or branched nature of the polymer. It is widely accepted that under these circumstances a decrease in the value of a indicates an increase in the degree of branching/hyperbranching.

[0126] D.sub.50this is a measure of grain size of the PVC and is determined thus. 12.5 g of resin is weighed and placed on a stack of six sieves having openings of 315, 250, 200, 160, 100 and 75 microns respectively, and a collecting pan for collecting anything that passes through the 75 micron sieve. The stack is secured to a vibrator and shaken for 15 minutes. The mass of resin in each sieve is recorded and each value divided by 12.5 to give a measure of the fraction of the total mass caught by that sieve. The values are plotted on a logarithmic graph and the value at which 50% of the mass is reached is determined.

[0127] GSDgrain size distribution. GSD is determined by using the graph obtained for the D.sub.50 grain size measurement to determine the grain size at which 16% of the mass of the resin is reached, and the grain size at which 84% of the mass of the resin is reached. The GSD is then calculated by halving the difference between the grain size at which 84% of the mass is reached and the grain size at which 16% of the mass is reached and dividing that result by D.sub.50.

[0128] BDbulk density. A quantity of resin is placed in a fluid bed dryer and dried at 50 C. for an hour. The resin is cooled for an hour. The resin is then poured through a funnel into a stainless steel container of precisely 100 cm.sup.3, conforming to ASTM 1895B. A sharp blade is used to level the resin mound, and the container weighed. The BD (bulk density) is calculated from the mass and volume of the resin in the container.

[0129] CPAthe CPA (cold plasticiser absorption) of the PVC may be determined by carefully weighing 2.5 g of the resin and 4 g dioctyl phthalate (a plasticiser) into a vessel containing a membrane. The vessel is jacketed and centrifuged at 3000 rpm for an hour (to give same value as the ASTM standard). The vessel is reweighed to determine the mass of plasticiser that has been adsorbed by the resin. A percentage figure relative to the mass of the resin can be calculated.

[0130] PFthe packing fraction of the PVC is a measure of how well the grains of resin pack together. It is calculated thus:

[00002]$\mathrm{PF}=\frac{\left(1+0.014.Math..Math.\mathrm{CPA}\right).Math.\left(0.1.Math..Math.\mathrm{BD}\right)}{1.4}$

[0131] Before testing, all samples of resin were washed twice with 1% (w/w) sodium lauryl sulphate and dried overnight in an oven at 50 C. The resin is then weighed, placed in the oven for a further hour and then re-weighed. Only when the mass no longer decreases by more than 1.0 g is it considered dry enough for testing.

[0132] The present invention will now be described by way of example only.

[0133] All materials were used as supplied without further purification. All materials were obtained from Aldrich apart from AIBN (from Pergan GmbH), IPA (from Fisher Scientific), methanol (from Brenntag GmbH or Mitsui & Co. Europe PLC) and VAc (from Brenntag GmbH or LyondellBasell Industries N.V.). Examples of the method of the present invention were performed by solution polymerisation and suspension polymerisation. Firstly, examples of the method of the present invention using solution polymerisation will be described

[0134] AGeneral Method Used for the Production of PVAc Using Solution Polymerisation

[0135] The monofunctional monomer (typically vinyl acetate), multifunctional monomer (in this case, TTT), initiator (typically AIBN), solvent (methanol and/or IPA) and CTA (typically propanal) were mixed in a reactor flask (typically a 1 litre flask) and deoxygenated with nitrogen for 30 minutes. The mixture was then heated to a reaction temperature (typically 70 C.). If further components are to be added (such as CTA), they are typically added over the following hour (although this period may be longer than an hour). The reaction was then held at the reaction temperature for a further 4 hours (making a total of 5 hours at the reaction temperature). Excess liquid was then removed by distillation, with a constant feed of methanol being added for 4 hours to maintain workable viscosities.

[0136] BProduction of PVOH from PVAc

[0137] The PVAc made by the method generally described above in A was hydrolysed using a 45% (w/w) solution of the PVAc in methanol. Typically, 14 mL of catalyst (10% (w/w) NaOH in methanol) was used per 100 g of polymer. Sometimes it is necessary to use larger amounts of catalyst (e.g. up to 20 mL of catalyst (10% (w/w) NaOH in methanol) per 100 g of polymer). Hydrolysis of PVAc to PVOH using a solution of sodium hydroxide (NaOH) is well-known to those skilled in the art for example GB749458, and it is described in Polyvinyl alcohol developments, Edited by C. A. Finch, (C) 1992 John Wiley & Sons Ltd, Chapter 3:Hydrolysis of Polyvinyl Acetate to Polyvinyl Alcohol, by F. L. Marten; C. W. Zvanut, p 57-77. The claims of the present application may incorporate any of the features disclosed in those documents. In particular, the claims of the present application may be amended to include features relating to the hydrolysis of the ester monomer residues on the polymer chain described in these documents.

[0138] For the avoidance of doubt the use of the description polyvinyl alcohol also encompasses poly(vinyl alcohol) and partially hydrolysed poly(vinyl acetate) and partially hydrolysed polyvinyl acetate and PVOH.

[0139] For the avoidance of doubt the use of the description polyvinyl acetate also encompasses poly(vinyl acetate) and PVAc.

[0140] Examples of polyvinyl acetate polymers made using the general method described above in A are now described with reference to Table 1. Examples labelled C. Ex are comparative examples, and are not within the scope of the present invention.

[0141] The solvent was IPA and/or methanol. The CTA was propanal, all of which was initially present in the reaction mixture i.e. no delayed addition of the CTA. The reaction time was 5 hours and the reaction temperature was 70 C.

[0142] The Examples above illustrate that satisfactory conversion levels could be obtained, but that appreciable levels of IPA were needed in order to inhibit gelling, given the amounts of CTA and TTT present in the reaction mixture.

TABLE-US-00001 TABLE 1 TTT:VAc Propanal:VAc Example m.sub.IPA m.sub.MeOH (mol:mol), (mol:mol), Conversion. M.sub.n M.sub.w No. (g) (g) % % (%) K-value g .Math. mol.sup.1 g .Math. mol.sup.1 PDI 1 150 0 0.17 0.51 82 14.3 3300 10500 3.2 C. Ex. 1 150 0 0.00 0.50 82 14.0 2800 9100 3.2 2 75 75 0.17 0.51 81 15.0 5200 18000 3.4 3 52 52 0.17 0.51 92 26.0 11300 115000 10.2 4 0 150 0.17 0.51 Gelled ND ND 5 38 113 0.17 0.51 87 28.0 125.0 118.5 9.5 6 26 78 0.17 0.51 Gelled ND ND 7 38 66 0.17 0.51 Gelled ND ND 8 26 78 0.17 0.76 89 55.1 9 26 78 0.33 1.01 Gelled ND ND 10 52 52 0.33 1.01 Gelled ND ND 11 52 52 0.33 2.03 Gelled ND ND 12 52 52 0.25 1.01 Gelled ND ND ND is not determined, due to gelation

[0143] Further examples are now described with reference to Table 2, illustrating that delayed addition of the CTA inhibits gelling.

TABLE-US-00002 TABLE 2 Example Propanal.sub.ini Propanal.sub.del IPA.sub.ini MeOH.sub.ini MeOH.sub.del TSC No. (R) (R) (R) (R) (R) (%) K-value 13 1.28 64.7 194 47.4 55 14 1.92 64.7 194 46.2 56 15 1.92 64.7 144 50 Gelled 16 0.96 1.92 64.7 144 50 44.6 58 17 0.96 3.84 64.7 144 50 44.5 53 18 2.88 7.68 64.7 144 50 45.5 45 19 3.46 12.0 51.8 144 50 41.8 31 20 4.04 14.0 38.8 144 50 45.6 40 21 4.04 14.0 19.4 144 50 39.6 53 22 4.85 16.8 164 50 36.6 54 23 4.85 16.8 144 50 Gelled 24 5.82 20.2 164 50 Gelled 25* 6.79 23.5 164 50 Gelled 26 6.79 23.5 164 50 44.4 32 *No control of propanal feed rate

[0144] The polymers of Table 2 were synthesised using the general method described above. IPA.sub.ini, MeOH.sub.ini and Propanal.sub.ini refer to the amount of IPA, methanol and propanal initially in the reaction mixture. 248.8 g of VAc, 1.20 g of TTT and 9.5 g of AIBN were also initially present in the reaction mixture. Further propanal (Propanal.sub.del) was added continuously (along with methanol, labelled MeOH.sub.del) over a period of an hour after the reaction mixture had been brought up to reaction temperature.

[0145] The Examples of Table 2 illustrate that it is possible to obtain polymers which are not gelled, even in the absence of IPA or with little IPA present, by delaying the addition of at least some of the CTA. The Examples of Table 2 illustrate that controlled addition is preferred; in Example 25, the delayed addition of propanal is not controlled and gelling is observed, whereas in Example 26, the delayed addition of propanal is controlled and a gel is not formed. In the Examples above, methanol is a preferred solvent because it has a lower chain transfer constant than IPA, and therefore fewer solvent residues are incorporated into the polymer. This is desirable because it is desired to incorporate more CTA residues to increase the amount of carbonyl groups in the polymer.

[0146] Investigations were undertaken to determine the characteristics of polyvinyl alcohols made by the method generally described above in A and B. Examples of polyvinyl alcohols made will now be described with reference to Table 3. Unless stated otherwise, the vinyl acetate polymers of the examples of Table 3 were synthesised at 70 C., with 248.8 g VAc, 1.20 g TTT, 9.5 g AIBN and 6.79 g propanal and 213.9 g MeOH initially present in the reaction mixture, with 23.5 g propanal being added continuously to the reaction mixture over a period of an hour, with the reaction being maintained at the reaction temperature for the further 4 hours after the propanal had been added. The polyvinyl acetates so obtained were then hydrolysed to form polyvinyl alcohols.

TABLE-US-00003 TABLE 3 TTT:VAc Example (mol:mol), DH M.sub.n M.sub.w no. % K-value (mol %) UV.sub.280 UV.sub.320 g .Math. mol.sup.1 g .Math. mol.sup.1 PDI MH C. Ex. 2 0 26.0 81.0 6.50 0.75 4600 12900 2.8 0.62 0 32.0 75.5 4.37 0.75 6600 20400 3.1 0.64 C. Ex. 3 78.5 4.64 0.90 5900 18700 3.2 0.66 27 0.10 30.0 75.4 4.86 0.85 5800 37200 6.4 0.51 78.7 4.90 0.75 4900 33300 6.8 0.50 28 0.16 48.8 70.3 5.08 1.00 5900 81700 13.7 0.44 29 0.17 34.8 71.7 5.50 1.00 8500 91800 11.0 0.41 C. Ex. 4 0.17 52.0 74.0 1.05 0.80 4150 104500 25.0 0.41 80.0 0.85 0.75 3900 91800 23.0 0.43 30 0.17 43.5 74.4 6.50 1.40 5300 81200 16.0 0.42 77.0 6.25 2.50 5000 77500 15.0 0.44 31 0.17 31.5 75.4 6.40 0.65 5000 57800 11.5 0.43 81.3 6.80 1.00 4500 50800 11.2 0.45 32 0.20 32.0 73.5 7.60 1.75 5900 71400 12.0 0.39 33 0.24 40.8 72.0 7.85 1.50 4700 82200 17.0 0.41

[0147] C. Ex. 2No TTT, Propanal.sub.ini=5.82 g, Propanal.sub.del=20.6 g

[0148] C. Ex 3No TTT, VAc=300 g, Propanal.sub.ini=5.82 g, Propanal.sub.del=20.6 g

[0149] Ex. 27-0.7 g TTT

[0150] Ex. 28VAc=265 g, Propanal.sub.del=25 g

[0151] Ex. 29MeOH.sub.ini=163.9 g, MeOH.sub.del=50 g

[0152] C. Ex. 4IPA used instead of propanal, IPA.sub.ini=24.4 g, IPA.sub.del=100 g

[0153] Ex. 32MeOH.sub.ini=163.9 g, TTT=1.45 g, Propanal.sub.ini=8.5 g, Propanal.sub.del=24.5 g, MeOH.sub.del=50 g

[0154] Ex. 33TTT=1.7 g, aliquot addition addition of propanal (5.66 g at t=10-20-30-40-50-60 minutes)

[0155] The use of the subscript ini refers to the amount of a particular component initially present in the reaction mixture. The use of the subscript del refers to the amount of component which is subject to a delayed addition.

[0156] The parameters listed in Table 3 above were measured for the polyvinyl alcohols, apart from the K-values which were measured for the polyvinyl acetates.

[0157] The examples of Table 3 illustrate that it is possible to make polymers with a high TTT concentration by using a correspondingly large amount of CTA, with addition of at least some of that CTA being delayed and controlled. For example, for Example 38, 10.1 g of the propanal was added initially and 43 g then added over a period of about an hour. The examples of Table 3 further illustrate that increasing the amount of TTT increases the intensity of the UV absorption peak at 280 nm, indicating that the concentration of (CC).sub.2CO species increases with amount of TTT used. The intensity of the UV absorption peak at 320 nm does not increase appreciably with the amount of TTT used, indicating that the concentration of the (CC).sub.3CO species is not markedly increasing. Furthermore, the small peak observed at 320 nm is consistent with the white colouration of the polymer. The Mark-Houwink constant decreases with an increasing amount of TTT used, indicating that the increase in TTT is leading to a greater amount of branching.

[0158] Further experiments were performed to investigate the effect of making the polyvinyl acetate in a 4 litre reactor (as opposed to a 1 litre reactor).

TABLE-US-00004 TABLE 4 TTT:VAc 4% (w/w) Example (mol:mol), CTA:TTT Conversion DH viscosity No. % (mol:mol) Reactor (%) K-value (mol %) UV.sub.280 UV.sub.320 (mPa .Math. s) 34 0.17 108.4 4- 84 26 71.5 7.0 0.8 3.00 (rpt. Ex. 30) L/SP 74.9 7.8 0.8 80.2 8.5 1.0 C. Ex. 5 0.17 430.0 4- 74 44 74.8 0.6 0.4 4.27 (rpt. C. Ex. 4) L/SP 77.3 0.5 0.3 81.5 0.4 0.2 35 0.20 96.2 4- 86 28 73.5 8.4 1.0 2.87 (rpt. Ex. 32) L/SP 75.0 9.0 1.0 78.2 9.1 1.0 79.2 9.5 1.3 36 0.24 106.1 4- 86 26 72.0 8.5 1.0 2.68 L/SP 76.4 9.1 0.8 77.9 9.2 1.3 80.2 9.7 1.0 37 0.28 105.2 1- 85 22 72.8 8.7 1.3 2.18 L/SP 74.4 9.7 1.3 83.5 8.5 1.0 38 0.30 106.0 1- 83 26 74.5 12.3 1.3 2.35 L/SP 76.7 13.0 1.5 79.0 14.2 1.5

[0159] The polyvinyl acetates were made using the method generally described above in relation to the examples of Table 3. The polyvinyl acetates were then hydrolysed as described above in B. The intensity of the UV absorption peak at 280 nm increases with the amount of TTT used. The viscosities of the solutions of the polyvinyl alcohols are generally low indicating that the branched character of the polymer is retained after hydrolysis.

[0160] Six samples of polymer were submitted for GPC analysis.

TABLE-US-00005 TABLE 4A Example M.sub.n M.sub.w PDI MH 35 5,200 159,100 31 0.38 34 6,900 122,900 18 0.42 C. Ex. 5 6,500 380,500 59 0.43 36 6,000 133,000 22 0.40 37 5,100 114,300 22 0.39 38 5,500 337,600 61 0.42

[0161] Experiments were performed to determine whether the method described above could be adapted to use other tri-unsaturated monomers, instead of the tri-unsaturated monomer, TTT. Examples of polyvinyl alcohols made using diallyl maleate (DAM) will now be described with reference to Table 5.

TABLE-US-00006 TABLE 5 DAM:VAc 4% Example (mol:mol), CTA:DAM Conversion DH viscosity. No. % (mol:mol) (%) K-value (mol %) UV.sub.280 UV.sub.320 (mPa .Math. s) 38 0.30* 106.0 83 26 74.5 12.3 1.3 2.35 76.7 13.0 1.5 79.0 14.2 1.5 40 0.31 94.4 Gelled 41 0.31 110.3 Micro-gelled 42 0.31 135.7 91 30 75.4 14.2 1.0 2.20 76.6 14.7 1.0 79.6 14.8 1.0 *Ex. 38 - used TTT, not DAM

[0162] The polyvinyl acetates were made using the method generally described above. All reactions were performed at 70 C. with VAc=248.8 g, MeOH=214 g, AIBN=9.5 g and DAM=1.9 g. The CTA (propanal) was added over a period of an hour, and the reaction mixture was then kept at reaction temperature for a further period of 4 hours. The initial charges of propanal added at the start were 10.1 g, 10.1 g and 11.0 g for Examples 40, 41 and 42 respectively. A further amount of propanal (43.0 g, 47.6 g and 60.0 g for Examples 40, 41 and 42 respectively) was added over an hour.

[0163] It was observed that a larger amount of propanal is required to avoid gel formation when using DAM than when using TTT. The intensities of the UV.sub.280 absorption peak is slightly greater for the polymer made using DAM than for the polymer made using TTT, indicating a slightly greater concentration of (CC).sub.2CO moieties. The K-value of Ex. 42 (made using DAM) is greater than that of Ex. 38 (made using TTT), but the 4% viscosity measurements are similar, indicating that some branches have probably been cleaved during hydrolysis. The effect of a delayed feed of monofunctional monomer and optionally multifunctional monomer was investigated, the results being shown below in Table 6.

TABLE-US-00007 TABLE 6 Example Temperature Feed Conversion DH No. ( C.) (h) (%) K-value (mol %) UV.sub.280 UV.sub.320 43 60 3 72 31.5 71.5 7.6 1.5 44 65 3 Gelled ND ND ND 45 65 3 Microgel ND ND ND 46 70 3 38 47 70 2 38 <20.0 48 75 2 81 23.0 * ND ND 49 70 2 84 22.1 72.5 5.3 0.6 73.9 7.2 1.5 79.2 7.2 1.0 ND is not determined

[0164] Ex. 43Initial mixtureMeOH=250 g, VAc.sub.ini=200 g, TTT=1.2 g, AIBN=9.5 g, propanal.sub.ini=6.79 g. Delayed addition of propanal=33.8 g and VAc=100 g

[0165] Ex. 44Initial mixtureMeOH=250 g, VAc.sub.ini=200 g, TTT=1.2 g, AIBN=9.5 g and propanal.sub.ini=6.79 g. Delayed addition of propanal=25 g and VAc=100 g

[0166] Ex. 45Initial mixtureMeOH=250 g, VAc.sub.ini=200 g, TTT=1.2 g, AIBN=9.5 g and propanal.sub.ini=6.79 g. Delayed addition of propanal=25 g and VAc=50 g

[0167] Ex. 46-48Initial mixtureMeOH=250 g, VAc.sub.ini=50 g, AIBN=9.5 g and propanal.sub.ini=10.1 g. Delayed addition of propanal=43 g, TTT=2.15 g and VAc=199 g

[0168] Ex. 48required hydrolysis levels were not achieved.

[0169] Ex. 49Initial mixtureMeOH=250 g, VAc.sub.ini=50 g, AIBN=9.5 g and propanal.sub.ini=10.1 g. Delayed addition of TTT=2.15 g and VAc=199 g. Delayed addition of propanal=43 g separate from VAc and TTT delayed feed.

[0170] The feed time in each case indicates the time period over which the delayed components were added. The total reaction time (including the feed time) was 5 hours in each case. The many examples above illustrate the synthesis and properties of polyvinyl acetates and polyvinyl alcohols made using solution polymerisation.

[0171] The influence of the type of initiator on the polymer properties was investigated.

[0172] The polymers of Table 7 below were synthesised and characterised using the general method described above in A and B. The vinyl acetate polymers of the examples were typically polymerised at 70 C., with 248.8 g of VAc, 2.15 g of TTT, 10.1 g of propanal and MeOH (typically 214 g, but differs according to the example) initially present in the reaction mixture; with propanal=43 g being added continuously to the reaction mixture over a period of an hour. The polymerisation being maintained at the reaction temperature for a further 4 hours after all of the propanal had been added. The initiator and initiator charging method are described below. The polyvinyl acetates so obtained were then hydrolysed to polyvinyl alcohols in accordance with the general method described previously.

TABLE-US-00008 TABLE 7 I:Vac (mol:mol), Conversion DH 4% Example Initiator % (%) K-value (mol %) UV.sub.280 UV.sub.320 (mPa .Math. s) 101 AIBN 1.28 89 29 81.9 14.4 1.9 3.2 102 AIVN 1.44 89 29 77.41 12.8 1.2 2.8 103 .sup.tBP2EH 1.04 98 29 73.8 13.8 1.6 2.5 75.6 14 1.6 104 .sup.tBP2EH 0.8 93 29 72.2 14.6 1.7 2.5 105 .sup.tBP2EH 0.56 96 28 76.2 14.8 1.6 2.7 78.6 16.0 1.7 81.9 16.4 1.8 106 .sup.tBP2EH 0.32 87 26 75.5 15.6 1.6 2.6 80.5 17.0 2.0

[0173] I in third column indicates Initiator

[0174] In Examples 101 to 106 below, the subscript ini refers to the amount initially in the reaction mixture.

[0175] Ex. 101AIBN.sub.ini=4.94 g. AIBN=1.14 g added as 1 aliquot after 45 minutes polymerisation.

[0176] Ex. 102MeOH.sub.ini=209 g, AIVN.sub.ini=6.5 g. AIVN=1.5 g dissolved in 5 g MeOH added as 1 aliquot after 45 minutes polymerisation

[0177] Ex. 103.sup.tBP2EH.sub.ini=3.5 g. .sup.tBP2EH=1.5 g and further aliquots added after 45 minutes and 1 hour 30 minutes polymerisation, respectively

[0178] Ex. 104.sup.tBP2EH.sub.ini=3.5 g. .sup.tBP2EH=1.5 g added as 1 aliquot after 45 minutes of polymerisation. The unhydrolysed polyvinyl acetate of Ex. 104 had M.sub.n=3,700 g.Math.mol.sup.1, M.sub.w=334,900 g.Math.mol.sup.1, PDI=91, MH=0.42.

[0179] Ex. 105MeOH.sub.ini=194 g, .sup.tBP2EH.sub.ini=1.5 g. .sup.tBP2EH=2 g dissolved in 20 g MeOH were added in a delayed manner, but continuously over a period of 2 hours 30 minutes.

[0180] Ex. 106MeOH.sub.ini=194 g, .sup.tBP2EH.sub.ini=0.5 g. .sup.tBP2EH=1.5 g dissolved in 20 g MeOH were added in a delayed manner, but continuously over a period of 2 hours 30 minutes.

[0181] It can be seen from Table 7 that the use of different initiators, or different molar quantities of initiator on vinyl acetate, or a different protocol for the addition of the initiator, did not dramatically affect the properties of the polyvinyl acetates and the polyvinyl alcohols. The intensities of the UV.sub.280 absorption peak, the K-value and the 4% solution viscosity measurements were all similar, and similar to those described previously.

[0182] The examples of Table 7 illustrate that it is possible to make polymers which are not gelled and which maintain the properties of the final polyvinyl alcohols, using a variety of initiators capable of generating free radicals. Furthermore, sufficiently high UV absorbance values can be generated by either adding said initiator in the initial monomer charge, at the start of the polymerisation or by a combination of both initial and delayed charging of the initiator.

TABLE-US-00009 TABLE 7.1 Unhydrolysed polyvinyl acetate sample K Value M.sub.n g/mol M.sub.w g/mol PDI MH EX. 104 29 3,700 334,900 91 0.42

[0183] The data shown in Table 7.1 confirms the formation of a hyperbranched polyvinyl acetate.

The Effect of Changing the Chain Transfer Agent was Investigated.

[0184]

TABLE-US-00010 TABLE 8 CTA:VAc 4% Example CTA:TTT (mol/mol), Conversion DH viscosity No. (mol/mol) % (%) K-value (mol %) UV.sub.280 UV.sub.320 (mPa .Math. s) 104 106 31.6 98 29 72.2 14.6 1.7 2.5 108 83.8 25.0 92 41 73.2 13.4 1.6 3.1 76.1 14.1 1.7 79.2 14.4 1.9 109 106 31.6 95 <20 80.1 22.2 3.74 2.3 110 85.4 25.5 95 29 75.8 16.6 2.4 2.5 77.7 16.5 2.3 111 98.2 29.3 95 23 75.5 19.4 2.3 2.2 77.0 18.6 2.4

[0185] Ex. 104 and 108 used propanal, and Ex. 109 and 111 used butyraldehyde.

[0186] Ex. 104propanal.sub.ini=10.1 g, propanal.sub.del=43.0 g

[0187] Ex. 108propanal.sub.ini=8.0 g, propanal.sub.del=34.0 g

[0188] Ex. 109butyraldehyde.sub.ini=12.54 g, butyraldehyde.sub.del=53.4 g

[0189] Ex. 110butyraldehyde.sub.ini=10.1 g, butyraldehyde.sub.del=43.0 g

[0190] Ex. 111butyraldehyde.sub.ini=11.6 g, butyraldehyde.sub.del=49.5 g

[0191] The polyvinyl acetates were prepared using the general method described above. All reactions were performed at 70 C., with VAc=248.8 g, .sup.tBP2EH=3.5 g, TTT=2.15 g, MeOH=214 g and an initial amount of chain transfer agent (indicated by the subscript ini) initially present in the reaction mixture, with an amount of chain transfer agent (denoted by the subscript del) being added continuously to the polymerising reaction mixture over one hour. The polymerisation reaction being maintained at 70 C. for a further 4 hours after all of the chain transfer agent had been added. An aliquot of 1.5 g of .sup.tBP2EH was added after 45 minutes polymerisation.

[0192] The results shown in Table 8 indicate that the intensity of the UV.sub.280 absorption peak considerably increased when butyraldehyde was substituted for propanal as the chain transfer agent (on an equivalent molar basis). Without being bound by theory, this observation indicates that a greater concentration of the desired (CC).sub.2CO moieties are present when butyraldehyde is used. The K-values and 4% solution viscosity values obtained for Ex. 109 and Ex. 110 (made using butyraldehyde) were lower than those of Ex. 107 and Ex. 108 (made using propanal) respectively. Without being bound by theory, this is consistent with more chain transfer reactions occurring with butyraldehyde.

TABLE-US-00011 TABLE 8.1 Unhydrolysed polyvinyl acetate sample K Value M.sub.n g/mol M.sub.w g/mol PDI MH EX. 111 29 4,600 142,900 91 0.42

[0193] The data shown in Table 8.1 confirms the formation of a hyperbranched polyvinyl acetate.

[0194] Different polymerisation protocols were investigated using the general methodology described above in A and B.

TABLE-US-00012 TABLE 9 4% CTA:TTT Temp. Feed Conversion DH viscosity Example (mol/mol) ( C.) (hours) (%) K-value (mol %) UV.sub.280 UV.sub.320 (mPa .Math. s) 112 72.9 70 1 92 34.5 75.1 12.4 1.9 3.8 76.6 12.1 1.7 80.4 13.3 2 113 65.7 70 1 100 40 73.8 11.5 1.7 3.8 77.8 12 1.7 80.8 12.6 1.7 114 85.8 70 1.5 97 31 70.8 10.2 1.3 3.2 78.3 11.5 1.5 80.9 12.4 1.2 115 61.1 70 1.5 98 48 ~72 8.2 1.4 5.1 75.8 9.1 1.5 79.9 9.1 1.4 116 106.0 70 1 98 27 73.7 14.5 2.1 3.0 77.7 14.6 2.2 80.8 14.7 2.1 117 63.7 70 2.5 91 29.5 73.0 12.6 1.9 2.9 76.3 11.9 1.6 79.7 13.7 2.0 118 67.9 70 1.5 92 48 71.8 9.8 2.1 4.1 75.7 10.8 2.2 77.7 10.6 2.1 80.8 10.9 2.0

[0195] Ex. 112Initial mixture of MeOH=200 g, VAc.sub.ini=100 g, TTT.sub.ini=0.7 g, .sup.tBP2EH.sub.ini=3.5 g. .sup.tBP2EH=1.5 g was added after 45 minutes polymerisation. Delayed addition of MeOH=14 g, TTT=1.45 g and VAc=148.8 g which was added over the 1 hour period after the start of polymerisation. Delayed addition of propanal=36.5 g over the 1 hour period after the start of polymerisation, and separate from the VAc and TTT delayed feed.

[0196] Ex. 113Initial mixtureMeOH=214 g, VAc.sub.ini=100 g, =T.sub.ini=0.7 g, .sup.tBP2EH.sub.ini=3.5 g. .sup.tBP2EH=1.5 g was added as an aliquot after 45 minutes of polymerisation. Delayed addition of TTT=1.45 g and VAc=148.8 g which was added over the 1 hour period after the start of polymerisation. Delayed addition of propanal=32.9 g over the 1 hour period after the start of polymerisation, and separate from the VAc and TTT delayed feed.

[0197] Ex. 114Initial mixtureMeOH=210 g, VAc.sub.ini=248.8 g, =T.sub.ini=0.71 g, .sup.tBP2EH.sub.ini=3.5 g. .sup.tBP2EH=1.5 g was added as an aliquot after 45 minutes polymerisation. Multiple additions of TTT=0.72 g in 2 g MeOH were made, one after 45 minutes and one after 1 hour 15 minutes after the start of polymerisation. Delayed addition of propanal=43 g was made over a period of 1 hour 30 minutes after that start of polymerisation.

[0198] Ex. 115Initial mixtureMeOH=210 g, VAc.sub.ini=248.8 g, =T.sub.ini=0.71 g, .sup.tBP2EH.sub.ini=3.5 g. .sup.tBP2EH=1.5 g was added as an aliquot after 45 minutes polymerisation. Multiple additions of TTT=0.72 g in 2 g MeOH were made, one after 45 minutes and one after 1 hour 15 minutes after the start of polymerisation. Delayed addition of propanal=30.6 g was made over a period of 1 hour 30 minutes after the start of polymerisation.

[0199] Ex. 116Initial mixtureMeOH=196.2 g, VAc.sub.ini=248.8 g, .sup.tBP2EH.sub.ini=3.5 g. .sup.tBP2EH=1.5 g was added after 45 minutes polymerisation. Delayed addition of MeOH=21.4 g and TTT=2.15 g was made over the period of 1 hour after the start of polymerisation. Delayed addition of propanal=43 g was also made over the period of 1 hour after the start of polymerisation, separate from the TTT delayed feed.

[0200] Ex. 117Initial mixtureMeOH=856 g, a mixture was formed of VAc=995.2 g, TTT=8.6 g, .sup.tBP2EH=14 g, propanal=127.6 g. 20 wt % of the mixture was initially charged to the reactor, before the start of the polymerisation, with the remaining 80% of the mixture added as a delayed addition over 2 hours 30 minutes. The batch was then cooked for 2 hours 30 minutes at 80 C.

[0201] Ex. 118Initial mixtureMeOH=210 g, VAc.sub.ini=248.8 g, =T.sub.ini=0.71 g, .sup.tBP2EH.sub.ini=3.5 g. .sup.tBP2EH=1.5 g was added as an aliquot after 45 minutes polymerisation. Multiple additions of TTT=0.72 g in 2 g MeOH were made, one after 45 minutes and one after 1 hour 15 minutes after the start of polymerisation. Delayed addition of propanal=34.0 g was made over a period of 1 hour 30 minutes after that start of polymerisation.

TABLE-US-00013 TABLE 9.1 Unhydrolysed polyvinyl acetate Sample K Value M.sub.n g/mol M.sub.w g/mol PDI MH EX. 115 48 8,800 1,428,700 162 0.44 Ex. 118 48 6,900 1,029,500 149 0.43

[0202] The data shown in Table 9.1 confirms the formation of a hyperbranched polyvinyl acetate.

[0203] Further examples of polymers of the present invention were synthesised using a suspension polymerisation process.

CSuspension Polymerisation to Form PVAc

[0204] 1200 g of H.sub.2O, 216 g of salt, 1.36 g of cellulose ether, 0.44 g of sodium carbonate, 4.44 g of tetrasodium pyrophosphate, 7.28 g of sodium bicarbonate, 0.4 ml of formic acid and 0.6 mL of defoamer were charged and mixed in the 4 litre reactor at 30 C. over 30 minutes. A solution of 900 g of VAc, 5.8 g of TTT and 89.8 g of propanal was added and water bath increased to 59 C. After 10 minutes at 59 C., 35 g of AIBN solubilised in 100 g of VAc was added and temperature set at 72 C. After the end of reflux, the suspension was maintained at 88 C. for 30 minutes, then distilled at 120 C. for 1 hour 45 minutes. Once the reaction cooled to 40 C., 44 g of salt was added and the reaction media stirred for 1 hour, before cooling.

DFormation of PVOH from PVAc Made by Suspension Polymerisation

[0205] The beads made in accordance with C above were extracted, washed with water and dried overnight. A solution was prepared by dissolving the bead in methanol at 45% (w/w). This solution was then used for hydrolysis, using 14 mL of methanolic sodium hydroxide (10% (w/w)) (as described above in relation to solution polymerisation) for 100 g of polymer.

[0206] The Example of Table 10 illustrates the production of PVAc and PVOH using a suspension polymerisation process.

TABLE-US-00014 TABLE 10 4% Example CTA:TTT DH viscosity. No. (mol/mol) CTA K-value (mol %) UV.sub.280 UV.sub.320 (mPa .Math. s) 53 66.5 Propanal 28 70.0 13.1 1.6 2.45

[0207] The example of table 10 illustrates that it is possible to make polyvinyl acetates and polyvinyl alcohols of the present invention using suspension polymerisation.

[0208] Furthermore, no delayed feed of CTA is required in order to prevent gelling. Without being bound by theory, this may be the result of the relatively high solubility of propanal in water which reduces the contact between the CTA and the monomers.

[0209] Some of the polyvinyl alcohol examples described above were used as a primary suspending agent in a suspension PVC polymerisation process, either in a 1 litre reactor or in a 10 litre reactor.

1 Litre Reactor Conditions

[0210] Various samples of a poly(vinyl chloride) composition were prepared on the basis of the following recipe:

TABLE-US-00015 TABLE 11 Demineralised water 350 g Vinyl chloride monomer 189 g Di (4-tert-butylcyclohexyl) 1,000 ppm (w/w) peroxydicarbonate solids on vinyl chloride Primary suspending agent 1,300 ppm (w/w) solids on vinyl chloride Secondary suspending agent Alcotex 552P 0-450 ppm (supplied by Synthomer (UK) Ltd.), (w/w) solids on partially hydrolysed poly(vinyl acetate) vinyl chloride having a degree of hydrolysis of about 55 mole % and a random distribution of acetate groups, 40% (w/w) aqueous solution Sodium bicarbonate (1% (w/w) solution in 800 ppm (w/w) demineralized water) solids on vinyl chloride

[0211] Demineralised water, suspending agents, buffer and initiator were all charged to a 1 litre Bchi stainless steel reactor (which had been previously coated with Alcotex 225 Build-Up suppressant supplied by Synthomer (UK) Ltd.) and assembled onto the rig. The recipe in Table 11 was designed to give a final grain size that was consistent with a typical commercial product. The reactor was then pressure tested, degassed to atmospheric and then vinyl chloride monomer charged via a volumetric bomb under nitrogen pressure. A suspension of vinyl chloride was prepared under stirring with about 750 rpm. The reactor was then heated within 6 minutes under agitation at 750 rpm to the desired polymerisation temperature within the range of 57 C., stirring at about 750 rpm was continued, the maximum pressure was recorded and the reaction stopped after a pressure drop of 0.2 MPa (by cooling and degassing to atmospheric pressure). The reactor was then subjected to a vacuum of approximately 50 kPa for 45 minutes. The reactor contents were then decanted in to a filter funnel and washed twice with 1% (w/w) sodium lauryl sulphate solution (as an anti-static treatment). The sample was then placed in a circulating fan oven at 50 C. for 12 hours to dry. A PVC analysis was then carried out and the results are shown in Table 12.

[0212] The results obtained in the 1 litre reactor are shown below in Table 12.

TABLE-US-00016 TABLE 12 PVOH used as primary TTT:VAc suspending (mol:mol) DH D.sub.50 CPA BD agent % (mol %) UV.sub.280 UV.sub.320 (m) GSD (%) (g/L) PF C. Ex. 6 0.00 73.0 5.7 4.6 125 0.25 18.7 516 46.5 C. Ex. 7 0.00 80.0 0.1 0.05 162 0.53 13.1 649 54.9 C. Ex. 3 0.00 75.5 4.4 0.9 198 0.23 24.8 467 44.9 C. Ex. 3 0.00 78.5 4.6 0.9 232 0.62 16.2 504 44.2 Ex. 27 0.10 75.4 4.9 0.9 166 0.23 15.2 522 45.3 Ex. 27 0.10 80.5 5.5 0.9 191 0.28 11.5 570 47.3 C. Ex. 4 0.17 74.2 0.8 0.8 163 0.25 16.7 506 44.6 C. Ex. 4 0.17 74.2 0.8 0.8 148 0.28 20.8 505 46.5 C. Ex. 4 0.17 80.6 0.8 0.8 128 0.23 10.5 543 44.5 C. Ex. 4 0.17 80.6 0.8 0.8 157 0.28 13.8 539 48.5 Ex. 30 0.17 74.4 6.5 1.4 127 0.21 16.4 519 45.6 Ex. 30 0.17 74.4 6.5 1.4 125 0.27 25.2 488 47.1 Ex. 30 0.17 77.1 6.5 2.5 117 0.29 13.2 545 46.1 Ex. 32 0.20 73.5 7.6 1.8 119 0.27 17.4 508 45.1 Ex. 32 0.20 73.5 7.6 1.8 107 0.32 21.6 507 47.2 Ex. 33 0.24 72.0 7.9 1.5 137 0.31 20.1 524 47.9 Ex. 33 0.24 72.0 7.9 1.5 120 0.30 23.0 504 47.6 104 0.3 72.2 14.6 1.7 121 0.27 24.4 468 44.9 108 0.3 73.2 13.4 1.6 123 0.24 17.2 567 50.2 108 0.3 76.1 14.1 1.7 90 0.73 14.0 576 49.2 111 0.3 75.5 19.4 2.3 121 0.27 27.3 463 45.8 111 0.3 77.0 18.6 2.4 110 0.30 12.2 610 51.0 112 0.3 75.1 12.4 1.9 115 0.31 20.0 543 49.7 113 0.3 73.8 11.5 1.7 114 0.29 16.0 568 49.6 113 0.3 77.8 12.0 1.7 92 0.79 13.0 613 51.7 114 0.3 70.8 10.2 1.3 119 0.27 25.6 507 49.2 114 0.3 78.3 11.5 1.5 123 0.25 20.2 492 45.1 115 0.3 75.8 9.1 1.5 116 0.28 14.4 567 48.7 116 0.3 73.7 14.5 2.1 117 0.29 16.0 577 50.5 117 0.3 73.0 12.6 1.9 136 0.27 23.4 521 49.38 118 0.3 71.8 9.8 2.1 119 0.26 14.0 566 48.3 118 0.3 75.7 10.8 2.2 122 0.29 12.6 596 50.1 118 0.3 77.7 10.6 2.1 93 0.77 10.8 606 49.8 C. Ex. 6 = Alcotex B72 - available from Synthomer (UK) Limited C. Ex. 7 = Alcotex 80 - available from Synthomer (UK) Limited

[0213] Those skilled in the art will realise that the TTT:VAc, DH, UV.sub.280 and UV.sub.320 used in Tables 12 and 13 refer to the properties of the PVOH used as a suspending agent, and that D.sub.50, GSD, CPA, BD and PF are properties of the polyvinyl chloride (PVC).

10 litre Reactor Conditions

[0214] The monomer was vinyl chloride. The example PVOH was added at 1300 ppm. No secondary suspending agent was used. The buffer was 200 ppm (as a 1% (w/w) sodium bicarbonate solution). The initiator was 1000 ppm di(4-tert-butylcyclohexyl) peroxydicarbonate. The reaction temperature was 57 C., in a 10 litre stainless steel reactor vessel coated with Alcotex 225 Build-up suppressant, with a standard stirrer operating at a stirrer speed of 600 rpm.

[0215] The results obtained using the 10 litre reactor are shown below in Table 13.

TABLE-US-00017 TABLE 13 PVOH used as primary TTT:VAc suspending (mol:mol), DH D.sub.50 CPA BD agent % (mol %) UV.sub.280 UV.sub.320 (m) GSD (%) (g/L) PF C. Ex. 6 0.00 73.0 5.7 4.6 132 0.26 29.2 498 50.2 C. Ex. 8 0.00 72.5 3.6 1.5 180 0.24 27.8 504 50.0 C. Ex. 9 0.00 78.0 3.7 1.7 168 0.32 23.6 511 48.6 C. Ex. 5 0.17 74.8 0.6 0.4 205 0.39 24.7 521 50.5 Ex. 36 0.24 72.0 8.5 1.0 138 0.42 24.5 495 47.6 Ex. 36 0.24 76.4 9.1 0.8 133 0.28 24.4 522 50.0 Ex. 36 0.24 74.9 7.8 0.8 119 0.63 21.8 493 45.9 C. Ex. 5 0.17 77.3 0.5 0.3 173 0.34 26.7 535 52.5 Ex. 38 0.30 74.5 12.3 1.3 100 0.31 28.2 494 49.2 C. Ex. 8 = Alcotex 72.5 - available from Synthomer (UK) Limited C. Ex. 9 = Alcotex 78 - available from Synthomer (UK) Limited

[0216] The data from Tables 12 and 13 suggest that the polyvinyl alcohols of the present invention performed successfully as primary suspending agents in the production of PVC.

[0217] The data further indicate that the polyvinyl alcohols of the present invention have a positive effect on reducing the grain size of the PVC. Without wishing to be bound by theory, this is expected to be associated with both the highly branched nature of the polyvinyl alcohol and with the presence of (CC).sub.2CO moieties. Indeed, there appears to be an inverse correlation between the intensity of the UV.sub.280 peak and the grain size as measured by D.sub.50 i.e. the greater the intensity of the UV.sub.280 peak, the smaller the polymer grain size. Furthermore, the polyvinyl alcohols of the present invention are typically white, or off-white, not yellow, orange or brown. This lack of colouration may be desirable.

[0218] Whilst the present invention has been described and illustrated with reference to particular embodiments, it will be appreciated by those of ordinary skill in the art that the invention lends itself to many different variations not specifically illustrated herein. By way of example only, certain possible variations will now be described.

[0219] The polymers of the examples above are made from one monofunctional monomer and one multifunctional monomer. Those skilled in the art will realise that more than one monofunctional monomer and/or more than one multifunctional monomer may be used.

[0220] The examples above illustrate the use of vinyl acetate as the monofunctional monomer. Those skilled in the art will realise that other monofunctional monomers (such as acrylates) could be used as comonomers.

[0221] Likewise, multifunctional monomers other than those described above in the examples could be used.

[0222] The examples above illustrate the use of propanal or butyraldehyde as the chain transfer agent. Other carbonyl-group containing chain transfer agents could be used.

[0223] The PVC polymerisation examples demonstrated in the present application are of a type known as cold charged, with the primary and secondary suspending agents being present at the beginning of the charging sequence. Other methods are known. Usually, water, protective colloid(s) and further optional additives are charged to the reactor first and then the liquefied vinyl chloride monomer and optional comonomer(s) are added. Optionally, the charging of the protective colloid may be simultaneous with the vinyl chloride monomer into a pre-heated reactor containing some or all of the aqueous phase. Optionally, the charging of the protective colloid may be simultaneous with some or all of the hot demineralised water which forms the aqueous phase in such a way that by the time the water, colloid(s) and monomer (such as vinyl chloride) are charged the reactor is at or near to the desired polymerisation temperature. This process is known as hot charging. Optionally, the initiator is then charged to the reactor.

[0224] Furthermore, it is well known in the state of the art that polyvinyl alcohols which can be used as primary suspending agents in PVC polymerisation can also be used to stabilise initiator dispersions which can be used in PVC polymerisations, for example see WO9818835

[0225] The polyvinyl alcohol primary suspending agent may be used in conjunction with other protective colloids, such as other primary protective colloids and with secondary and tertiary protective colloids. Specific examples of protective colloids are listed in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, 1992, page 722, Table 3.

[0226] Where in the foregoing description, integers or elements are mentioned which have known, obvious or foreseeable equivalents, then such equivalents are herein incorporated as if individually set forth. Reference should be made to the claims for determining the true scope of the present invention, which should be construed so as to encompass any such equivalents. It will also be appreciated by the reader that integers or features of the invention that are described as preferable, advantageous, convenient or the like are optional and do not limit the scope of the independent claims. Moreover, it is to be understood that such optional integers or features, whilst of possible benefit in some embodiments of the invention, may not be desirable, and may therefore be absent, in other embodiments.