Low-salt process for the preparation of a polysulfide

Abstract

Process for the preparation of a polysulfide comprising the step of reacting in the absence of a dihaloalkane a bis(2-dihaloalkyl)formal in the presence of (i) a pre-polymer (I) according to structure (I)
X(R2O)nCH2O(R1O)mCH2(OR2)pX(I),
wherein R1 and R2 can be the same or different and are selected from alkane chains containing 2-10 carbon atoms, X is a halogen atom, and n, m, and p are integers that can be the same or different and have a value in the range 1-6, with either (i) sodium polysulfide or (ii) a combination of sodium hydrosulfide and sulfur.

Claims

1. Process for the preparation of a polysulfide comprising the step of reacting a bis(2-haloalkyl)formal with either (i) sodium polysulfide or (ii) a combination of sodium hydrosulfide and sulfur, the reaction being performed in the absence of a dihaloalkane and in the presence of a pre-polymer (I) according to structure (I)
X(R.sup.2O).sub.nCH.sub.2O(R.sup.1O).sub.mCH.sub.2(OR.sup.2).sub.pX(I), wherein R.sup.1 and R.sup.2 can be the same or different and are selected from alkane chains containing 2-10 carbon atoms, X is a halogen atom, and n, m, and p are integers that can be the same or different and have a value in the range 1-6.

2. Process according to claim 1, wherein the bis(2-haloalkyl)formal is bis(2-chloroalkyl)formal.

3. Process according to claim 1 wherein the X is a halogen selected from Cl, Br, and I.

4. Process according to claim 3 wherein the X is Cl.

5. Process according to claim 1, wherein the R.sup.1 of the pre-polymer (I) is CH.sub.2CH.sub.2.

6. Process according to claim 1, wherein the R.sup.2 of the pre-polymer (I) is CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2, or CH.sub.2CH.sub.2CH.sub.2CH.sub.2.

7. Process according to claim 1, wherein the product resulting from the reaction of the bis(2-haloalkyl)formal with sodium polysulfide in the presence of the pre-polymer (I) is treated with a reduction agent to obtain a liquid polysulfide.

8. Process according to claim 1, wherein the molar ratio of sodium polysulfide (calculated as Na.sub.2S.sub.x) relative to the bis(2-haloalkyl)formal is in the range 0.8-1.4.

9. Process according to claim 1, wherein a mixture comprising bis(2-haloalkyl)formal and the pre-polymer (I) is added to an aqueous solution of sodium hydrosulfide and sulfur.

10. Process according to claim 9, wherein the aqueous solution has a temperature in the range of 60 to 100? C.

11. Process according to claim 1, wherein the weight ratio of the bis(2-haloalkyl)formal to the pre-polymer (I) is in the range of 90:10 to 10:90.

12. Product obtained by the process according to claim 1.

13. A composition comprising a product obtained by the process according to claim 1, said composition selected from sealants, adhesives and coating compositions.

Description

(1) In one embodiment, the process of the invention is performed by first preparing a mixture comprising the bis(2-haloalkyl)formal, the pre-polymer, and optionally the branching agent, and adding this mixture to an aqueous solution of sodium polysulfide and alkali metal hydroxide whereby the process is performed in the absence of a dihaloalkane. Optionally, a dispersing agent, such as magnesium hydroxide, and/or a wetting agent (e.g. sodium butylnaphthalenesulfonate) may be present in the solution.

(2) The mixture is preferably added slowly, e.g. dropwise, to the solution. The temperature of the solution is preferably in the range 60 to 100? C., more preferably from 80 to 95? C. and most preferably from 85 to 90? C. This addition is preferably conducted for 20 minutes to 2 hours, more preferably 30 minutes to 1.5 hours and most preferably 30-60 minutes.

(3) In a second embodiment, the process of the invention is performed by first preparing a mixture comprising bis(2-haloalkyl)formal and the pre-polymer (I), and optionally the branching agent, and adding this mixture to an aqueous solution of NaHS and sulfur. This embodiment has the additional advantage of a simple process design. The bis(2-haloalkyl)formal-containing mixture is preferably added slowly, e.g. dropwise, to the NaHS and sulfur solution. The temperature of the NaHS and sulfur solution is preferably in the range 60 to 100? C., more preferably from 80 to 100? C. and most preferably from 90 to 100? C. Preferably, a phase transfer catalyst (PTC), such as a quaternary ammonium compound, is added to the mixture. A PTC according to the invention is a catalyst which facilitates the migration of a reactant from a first phase into a second phase, wherein the reaction occurs in the second phase. The polymer obtained in this embodiment is a liquid polysulfide.

(4) In a further embodiment, the process according to the invention is performed by adding the reactants (such as bis(2-chloroalkyl)formal, pre-polymer (I), (i) sodium polysulfide or (ii) a combination of sodium hydrosulfide and sulfur, PTC, the branching agent, the dispersing agent) to one single reactor, preferably sequentially. This embodiment has the additional advantage of a simple process design.

(5) As a subsequent step, the resulting reaction mixture is preferably treated with a desulfurization agent (e.g. sodium hydroxide and sodium hydrogen sulfide) to eliminate any labile sulfur atoms. This desulfurization step can be conducted at a preferred temperature of 80-110? C., more preferably 85-105? C., and most preferably 90-100? C. The reaction time is preferably 1-4 hours, more preferably 1-3 hours, and most preferably 1-2 hours.

(6) In case of reacting the bis(2-haloalkyl)formal in the presence of the pre-polymer (I) with sodium polysulfide according to the invention, the macromolecules in the resulting polysulfide polymer need to be reduced to the required chain length by reductive splitting of the disulfide bonds to obtain a liquid polysulfide. The most common reduction agents are sodium dithionite (Na.sub.2S.sub.2O.sub.4) and a combination of NaSH and Na.sub.2SO.sub.3. The amount of reduction agent to be used depends on the desired molecular weight, as commonly known in the art.

(7) The preferred reduction agent in the process according to the invention is sodium dithionite. Reductive splitting using sodium dithionite is preferably performed for 20-40 minutes. The temperature preferably ranges from 80 to 110? C., more preferably from 85 to 105? C. and most preferably from 90 to 100? C. The reaction time is preferably 1-4 hours, more preferably 1-3 hours, and most preferably 1-2 hours.

(8) If desired, the splitted disulfide bonds can then be converted into reactive terminal thiol groups by acidification at pH 4-5. Acetic acid is preferably used as the acidifier. Sulfuric acid, formic acid, and citric acid are also preferred acidifiers.

(9) As a last step, the polysulfide can be washed and dewatered under reduced pressure (preferably from 20 to 500 mbar).

(10) The polysulfide resulting from the process of the present invention has various applications, including the use as binder in sealants, adhesives, and coating compositions, in isocyanate cure, in epoxy-resin cure, and in acrylate resin cure.

EXAMPLES

(11) A. Pre-polymer (I) preparation of a pre-polymer (I) mixture based on triethylenglycole (TEG)

(12) A mixture of 4 moles paraformaldehyde (content: 90,5%, supplier Norkem B.V.), 7,5 moles technical ethylene chlorohydrin (ECH) with an average molecular weight of 83,5 g/mol (supplier: CBW Chemie GmbH Bitterfeld), 1 mol TEG (suuplier: Brenntag GmbH) and 5,4 g hydrochloric acid (37%) was heated in a 1,5 liter flask with stirring to about 60? C. until the paraformaldehyde was dissolved. The nearly clear reaction liquid was transferred to a flask of a distillation apparatus with a packed column and subjected to a two stage distillation.

(13) Stage 1: The flask content was gradually heated to 87? C. within 2,5 hours (h) at reduced pressure of 120 mbar. Stage 1 was finished when the head temperature of the distillation had reached 54? C. The Distillate was a mixture of 41% ECH, 58% water and 1% paraformaldehyde.

(14) Stage 2: The flask content resulting from stage 1 was further heated to 135? C. within 1 hour at reduced pressure of 20 mbar. Stage 2 was finished when the head temperature of the distillation had reached 94? C. The distillate was composed of 73% ECH, 8% water, 1,5% HCI and 17,5% bis-(2-chloroethyl)-formal.

(15) The resulting reaction product of 685 g was a mixture of 25% TEG based pre-polymer (I) according to the present invention, 40% bis-(2-chloroethyl)-formal and 35% homologue impurities derived from the pre-polymer (I) and bis-(2-chloroethyl)-formal.

(16) The mixture had a number average molecular weight M.sub.n of 233,1 g/mol and a chlorine content of 30,4 wt%. The chemical structure of the TEG based pre-polymer (I) was determined by means of GC-MS and NMR-spectroscopy.

(17) Example A2: Preparation of a pre-polymer (I) mixture based on diethylenglycole (DEG)

(18) A mixture of 4 moles paraformaldehyde, 6 moles technical ethylenchlorhydrin, 2 moles diethylene glycol (DEG) and 5,4 g hydrochloric acid (37%) was treated according to Example A1. 580 g reaction mixture consisting of 30% DEG based pre-polymer (I), 25% bis-(2-chloroethyl)- formal and 45% homologue impurities were obtained. The mixture had a number average molecular weight M.sub.n of 297,2 g/mol and a chlorine content of 23,9 wt %.

(19) The chamical structure of the DEG based pre-polymer (I) was determined by means of GC-MS and NMR-spectroscopy.

(20) Example A3: Preparation of bis-(2-chloroethyl)-formal (Comperative Example)

(21) A mixture of 4 moles paraformaldehyde, 10 moles technical ethylenchlorhydrin and 5,4 g hydrochloric acid (37%) was treated according to Example A1 without using a polyol as reaction component. 700 g bis-(2-chloroethyl)-formal and its homogues were obtained with a number average molecular weight M.sub.n of 179 g/mol and a chlorine content of 39,6 wt. %.

(22) The obtained mixture was composed of 80 % bis-(2-chloroethyl)-formal and 20% homogue impurities accordin to GC analysis.

(23) B. Polysulfide (PS) preparation

(24) Example B1: Preparation of a polysulfide using the TEG based pre-polymer (I) (A1)

(25) 1 Liter of an aqueous 2,2 mol/l Na.sub.2S.sub.x solution (x=2,4) was mixed under stirring in a 2,5 liter flask with 25,1 g 32 % MgCl.sub.2 solution, 12 g 50% NaOH solution and 10 ml 30% sodium butylnaphthalene-sulfonate solution and heated to 88? C. A mixture of 512,8 g (2,2 mol) TEG based prepolymer (I) (A1) and 6,5 g (0,044 mol) trichloropropane (TCP) was added within 1 hour while keepign the temperature between 88 and 92? C. After the dosage the reaction mixture was stirred for 30 min at 88-92? C. to complete the raction. Following 100 ml of a 5 molar aqueous Na.sub.2S solution were added. Thereafter, the mixture was heated and stirred for 2 hours at 100? C.

(26) After the reaction, the formed polysulfide latex was washed several times with warm water (50? C.) to remove any soluble salts generated during the condensation process.

(27) In a further step, the washed polysulfide latex was treated with 34 g 90 % sodiumdithionite (0,18 moles), 48,9 g 50 % NaOH solution (0,62 moles) and 66 g 40% sodiumbisulfite solution (0,25 moles) at 98? C. The reaction mixture was stirred for 30 min at 98? C. to complete the reduction process. Subsequently, the product was washed several times with warm water (50? C.) to remove any soluble salts from the polysulfide latex. Thereafter, the polysulfide latex was acidifed with acetic acid to pH 4-5 to coagulate the polysulfide. The coagulated polysulfide was dewatered under reduced pressure (90? C., 20 mbar). The resulting polysulfide was obtained as a viscous yellow brown liquid. The obtained polysulfide had a number average molecular weight M.sub.n in the range of 1800-2700 g/mol.

(28) TABLE-US-00001 TABLE B1 yield polysulfide 503.6 g measured: 478.4 g (= 95.0 % of (PS) (theory): theory) Cl-content/batch 166.7 g measured: 165.4 g (Amount of Cl in (theory): the waste water) Cl-emission/kg 331.0 g measured: 345.7 g PS (theory):

(29) The ratio of sulfur to oxygen in the obtained polysulfide was derived from the stoichiometry of the reactants as 1:1,7.

(30) Example B2: Preparation of a polysulfide using the DEG based pre-polymer (I) (A2)

(31) The reaction of Example B1 was carried out with 653,8 g (2,2 mol) DEG based pre-polymer (I) (A2) instead of the TEG based pre-polymer (I) (A1). The resulting polysulfide had a number average molecular weight M.sub.n in the range of 1800-2700 g/mol.

(32) TABLE-US-00002 TABLE B2 yield PS (theory): 644.6 g measured: 607.2 g (= 94.2 % of theory) Cl-content/batch 166.7 g measured: 163.9 g (Amount of Cl in (theory): the waste water) Cl-emission/kg 258.6 g measured: 270.0 g PS (theory):

(33) The ratio of sulfur to oxygen in the obtained polysulfide was derived from the stoichiometry of the reactants as 1:2,5.

(34) Comparative Example B3: Preparation of a polysulfide using the bis-(2-chlorethyl)-fomral (A3)

(35) The raction of Example B1 was carried out with 393,8 g (2,2 mol) bis-(2-chlorethyl)-formal (A3) instead of the TEG based pre-polymer (I) (A1). The resulting polysulfide had an average molecular weight in the range of 1800-2700 g/mol.

(36) TABLE-US-00003 TABLE B3 yield PS (theory): 384.6 g measured: 360.4 g (= 93.7 % of theory) Cl-content/batch 166.7 g measured: 166.2 g (Amount Cl in the (theory): waste water) Cl-emission/kg 433.4 g measured: 461.2 g PS (theory):

(37) The ratio of sulfur to oxygen in the obtained polysulfide was derived from the stoichiometry of the ractants as 1:1.

(38) The chloride emissions in the Examples B1 and B2 were 25% and 41% lower, respectively, compared with Comparative Example B3. Thus, the Examples B1 and B2 show an improved salt balance compared to the Comparative Example B3.

(39) The sulfur to oxygen ratio in the Examples B1 and B2 were higher in oxygen content in comparison to Example B3. Thus, the polysulfides prepared accordin to the invention (Examples B1 and B2) are more polar compared to the polysulfide obtained by the Comparative Example B3.

(40) C. Application testing of the polysulfide, produced in accordin gto Examples B1, B2, and Comparative Example B3.

(41) Sealant formulation

(42) Insulating glass sealant formulations were prepared using a conventional laboratory Butterfly mixer. The batch-size in all texts was approx. 1.5 kg.

(43) A number of plasticizers were selected depending on thier polarity relative to the polysulfide (B3). The plasticizers used in the following were: Diethylene Glycol Dibenzoate (DEG) (non-polar (np)) 3,3-oxydi-1-propanol dibenzoate (DPG) (polar (p)), a blend of DPG/DEG Dibezoate (1:1) (np), Alkyl (C7-C9) Benzyl Phthalate (p), Alkyl (C4) Benzyl Phthalate (p), Di-alkyl (C9) Phthalate (np), Chlorinated paraffin (chlorine content 45-55 wt%) (np).

(44) TABLE-US-00004 TABLE 1 Sealant formulation according to the invention: Polymer-Part Temp- Charging Time erature Raw Material [wt%] [min] [? C.] Remarks Butterfly-Mixer, under temp. and pressure control Polysulfides 20.0 20 Charging prepared according to Examples B1, B2 and Comparative Example B3 Plasticizer 11.7 Charging 10 25 intensive mixing at 800/min at 1 bar Omya 12.0 Charging Omyacarb 2 GU (natural calcium carbonate) 5 30 intensive mixing at 800/min at 1 bar 10 intensive mixing at 800/min at ?1 bar Solvay 8.3 Charging Winnofil SPM (precipitated carlcium carbonate) 5 45 intensive mixing at 800/min at 1 bar 10 intensive mixing at 800/min at ?1 bar Omya 47.4 Charging Omyacarb 6 AL (natural calcium carbonate) 5 55 intensive mixing at 800/min at 1 bar 10 intensive mixing at 800/min at ?1 bar Evonik 0.6 Charging Dynasilan Glymo (organosilane) 5 65 intensive mixing at 800/min at 1 bar 15 intensive mixing at 800/min at ?1 bar 65 Break vacuum and keep the batch for 1d at 25? C. before further testing

(45) TABLE-US-00005 TABLE 2 Sealant formulation according to the invention: Curative-Part Temp- Charging Time erature Raw Material [wt %] [min] [? C.] Remarks Butterfly-Mixer, under temp. and pressure control Honeywell 27.0 Max.: 45 Charging MnO.sub.2, Type FA Ferro 27.0 Max.: 45 Charging Santicizer 278 (high molecular weight phtalathic plasticizer) Eastman 27.0 Max.: 45 Charging Benzoflex 9-88 (benzoate based plasticizer) Water 0.5 Charging 15 Max.: 45 intensive mixing at 20/min at 1 bar Cabot Carbon 8.1 Charging Black, Type 465 15 Max.: 45 intensive mixing at 20/min at 1 bar Omya 5.5 Max.: 45 Charging Omyacarb 6 AL (natural calcium carbonate) Evonik 3.2 Max.: 45 Charging FK 320 (precipitated silica) 15 Max.: 45 intensive mixing at 20/min at 1 bar Several suppliers 1.3 Charging Tetramethy-Thiram- disulfide (TMTD) 15 Max.: 45 intensive mixing at 20/min at 1 bar Several suppliers 0.4 Charging N,N- Diphenylguanidin (DPG) 15 Max.: 45 intensive mixing at 20/min at 1 bar 15 intensive mixing at 20/min at ?1 bar Max.: 45 Tripple roll mill, milling to 20 micron particle size. Keep the batch for 1d at 25? C. before further testing

(46) The application behavior of the polysulfides B1 and B2 and the polysulfide of Comparative Example B3 were tested in an insulating glass sealant prepared according to Table 1 (Polymer-Part) and Table 2 (Curative-Part). Both parts were thoroughly mixed according the mixing ratio 100:9 by weight (Polymer-part: Curative-Part).

(47) Application test

(48) Application properties were determined of the sealants prepared accordin gto Table 1 and Table 2, with regard to Shore A (DIN _B 53505:2000) behavior after 24 hours and after 48 hours, and with regard to the Tensile test (Elongation) after 24 hours (DIN 53455:1981). All sealants contained DPG (p) as the plasticizer and 20 wt% of the polysulfide B1, B2, or B3, respectively. Testing was peformed on the sealants after aging for 1 day at 23? C. and 50% relative humidity (rH). (23? C. and 50% rH are also abbreviated with NL in Table 4).

(49) TABLE-US-00006 TABLE 3 Application test (Plasticizer DPG (p)) Results of sealant application testing containing 20 wt % polysulfide prepared according to Examples B1, B2 or Comparative Example B3, respectively Comparative Example B3 Example B2 Example B1 Ageing: 1d Ageing: 1d Ageing: 1d Test conditions 49/23 48/22 50/23 (% rel. Humidity (rH)./? C.) Viscosity of A 289 300 278 comp. @ 10 s.sup.?1 (Pas) Viscosity of B 30 30 30 comp. @ 10 s.sup.?1 (Pas) Mixing ratio by 9 9 9 weight 100 to Mixing ratio by 10 10 10 volume 100 to Pot life (min) 36 40 32 Tack free time 38 42 35 (min) Shore A Test (DIN 53505) Shore A (after 44 43 46 24 h NL) (5 s) Shore A (after 40 40 42 24 h NL) (3 min) Shore A (after 44 47 47 24 h 60 ? C.) (5 s) Shore A (after 41 43 44 24 h 60 ? C.) (3 min) Shore A (after 47 49 47 48 h 60 ? C.) (5 s) Shore A (after 43 46 44 48 h 60 ? C.) (3 min) Tensile test (Film 2 mm) after 24 h 23?/50% rH (DIN 53455) Modulus @ 10% 0.3 0.3 0.3 elongation (N/ mm.sup.2) Modulus @ 25% 0.5 0.5 0.6 elongation (N/ mm.sup.2) Modulus @ 50% 0.9 0.9 1.0 elongation (N/ mm.sup.2) Modulus @ 1.5 1.4 1.5 100% elongation (N/mm.sup.2) Tensile strength 1.5 1.5 1.5 (N/mm.sup.2) Elongation @ 105 114 97 break (%) Tensile test (Film 2 mm) 24 h 23?/50% rH + 24 h 60? C. (DIN 53455) Modulus @ 10% 0.3 0.3 0.3 elongation (N/ mm.sup.2) Modulus @ 25% 0.6 0.6 0.6 elongation (N/ mm.sup.2) Modulus @ 50% 1.0 1.0 1.0 elongation (N/ mm.sup.2) Modulus @ 0 1.6 0 100% elongation (N/mm.sup.2) Tensile strength 1.4 1.6 1.5 (N/mm.sup.2) Elongation @ 83 102 83 break (%)

(50) As can be seen from Table 3, the sealants containing the polysulfides B1 or B2, obtained by the low-salt process according to the invention, which process has a lower halogen content of the raction mixture compared to the process of Comparative Example B3, shows at least equivalent application preformance, such as Elongation and Shore A hardness of the sealant, compared to the sealant containing the polysulfide of Comparative Example B3.

(51) Compatibility of the sealant containing the polysulfides B1, B2, or B3 with plasticizers.

(52) The compatibility of the sealant prepared accordin to Table 1 and Table 2, containing the polysulfides of Examples B1, B2 or of Comparative Example B3, respectively, with different plasticizers was assessed by visual inspection of the cured sealant matrics comprising the polysulfide and the plasticizer. If no migration of plasticizer out of the matrix was observed, the polysulfide and the plasticizer were compatible. If migration was observed, the polysulfide and the plasticizer were incompatible. In addition, the cohesion or adhesion behavior (referred to in Table 4 as Adhesion behavior) of the sealant to glass substrate was evaluated in accordance to DIN 53504:2009. In this regard, adhesion means: no chemical adhesion; only physical adhesion and cohesion means: chemical adhesion. Cohesive behavior was desired.

(53) TABLE-US-00007 TABLE 4 Compatibility of the sealant containing the polysulfides B1, B2, or B3 with the plasticizers Sealant containing the polymer prepared according to Compatibility of sealant Example Example Example formulation to Plasticizer B3 B2 B1 Diethylene Glycol Dibenzoate (DEG) (np) Compatibitity to sealant Incompatible Compatible Compatible formulation Adhesion behaviour to Adhesive Cohesive Adhesive / glass substrate (p) Cohesive 3,3-oxydi-1-propanol dibenzoate (DPG) (p) Compatibitity to sealant Compatible Compatible Compatible formulation Adhesion behaviour to Cohesive Cohesive Cohesive glass substrate (polar (p)) Blend of DPG/DEG Dibenzoate (1:1) (np) Compatibitity to sealant Compatible Compatible Compatible formulation Adhesion behaviour to Adhesive Cohesive Cohesive glass substrate (p) Alkyl (C7-C9) Benzyl Phthalate (p) Compatibitity to sealant Compatible Compatible Compatible formulation Adhesion behaviour to Cohesive Cohesive Cohesive glass substrate (p) Alkyl (C4) Benzyl Phthalate (p) Compatibitity to sealant Compatible Compatible Compatible formulation Adhesion behaviour to Adhesive/ Cohesive Cohesive glass substrate (p) Cohesive Di-alkyl (C9) Phthalate (np) Compatibitity to sealant Incompatible Incompatible Incompatible formulation Adhesion behaviour to Adhesive Adhesive Adhesive glass substrate (P) Chlorinated paraffins (chlorine content 45-55 wt %) (np) Compatibitity to sealant Compatible Compatible Compatible formulation Adhesion behaviour to Cohesive Cohesive Cohesive glass substrate (P)

(54) As can be seen from Table 4, the sealants containing the polysulfides B1 or B2, prepared by the low-salt process according to the invention, show comparable compatibility and application properties (cohesion or adhesion behavior) compared to the sealant containing the polysulfide of Comparative Example 3.

(55) Cohesion or Adhesion of the sealant to polar (p) and non-polar (np) surfaces (Plasticizer DPG (p))

(56) The cohesion or adhesion behavior (referred to in Table 5 as Adhesion behavior) of the sealant prepared according to Table 1 and Table 2, containing the polysulfides of Examples B1 or B2 was compared to the sealant containing the polysulfide of Comparative Example B3 with regard to polar (p) and non-polar (np) surfaces. The polarity of a surface was established by determining the contact angle between a water drop and the contact surface (Reference norm is DIN EN 828:2013-04). A hydrophilic or polar surface (p) has a low contact angle (<90?) and a hydrophobic or non-polar surface (np) has a high cantact angle (>90?). The cohesion or adhesion behavior was assessed in accordance with DIN 53504:2009. The sealants contained the plasticizer DPG (p). The sealants were applied to the respective testing surface. The polymeric surfaces (PUR) were additionally cured after the application, prior to testing. Cohesive behavior was desired.

(57) TABLE-US-00008 TABLE 5 Sealant Adhesion behavior on different polar (p) and non-polar (np) surfaces Sealant containing the polymer prepared according to Example Example Example B3 B2 B1 Adhesion behaviour on polymeric surfaces [acc. DIN 53504] Polyurethanes (PUR) (OH- terminiated Polybutadiene)-based) (np) Modulus at 25% elonagtion [N/mm.sup.2] 0.4 0.6 0.5 Tensile strength [N/mm.sup.2] 1.2 1.5 1.4 Break-Type (Cohesive/Adhesive) Adhesive/ Cohesive Cohesive Cohesive Polyurethanes (PUR) (Polyether- based) (np) Modulus at 25% elonagtion [N/mm.sup.2] 0.4 0.6 0.5 Tensile strength [N/mm.sup.2] 1.5 1.6 1.5 Break-Type (Cohesive/Adhesive) Adhesive/ Cohesive Cohesive Cohesive Polyacrylates (PMMA) (p) Modulus at 25% elonagtion [N/mm.sup.2] 0.6 0.9 0.8 Tensile strength [N/mm.sup.2] 1.5 1.7 1.6 Break-Type (Cohesive/Adhesive) Adhesive/ Cohesive Cohesive Cohesive Polysulfides (Bis (2-chlorethyl) formal based) (p) Modulus at 25% elonagtion [N/mm.sup.2] 1.1 1.3 1.2 Tensile strength [N/mm.sup.2] 2.2 2.4 2.3 Break-Type (Cohesive/Adhesive) Cohesive Cohesive Cohesive Epoxies (EP) (p) Modulus at 25% elonagtion [N/mm.sup.2] 0.8 0.9 0.8 Tensile strength [N/mm.sup.2] 1.6 1.8 1.8 Break-Type (Cohesive/Adhesive) Cohesive Cohesive Cohesive Adhesion behaviour to inorganic/ metallic surfaces [acc. DIN 53504] Stainless steel (p) Modulus at 25% elonagtion [N/mm.sup.2] 0.9 1.1 1.1 Tensile strength [N/mm.sup.2] 0.5 1.9 1.8 Break-Type (Cohesive/Adhesive) Adhesive/ Cohesive Cohesive Cohesive Galvanized steel (p) Modulus at 25% elonagtion [N/mm.sup.2] 0.9 1.1 1.0 Tensile strength [N/mm.sup.2] 1.6 1.9 1.7 Break-Type (Cohesive/Adhesive) Cohesive Cohesive Cohesive Aluminium (anodized) (p) Modulus at 25% elonagtion [N/mm.sup.2] 0.7 1.1 1.0 Tensile strength [N/mm.sup.2] 1.4 1.9 1.7 Break-Type (Cohesive/Adhesive) Cohesive Cohesive Cohesive Glass (p) Modulus at 25% elonagtion [N/mm.sup.2] 0.9 1.1 0.9 Tensile strength [N/mm.sup.2] 1.9 2.0 1.9 Break-Type (Cohesive/Adhesive) Cohesive Cohesive Cohesive

(58) As can be seen from Table 5, the sealants containing polysulfides B1 or B2 show a constant cohesive behavior on a variety of polar surfaces. Even on the non-polar surfaces, the sealants containing polysulfides B1 or B2 according to the invention show cohesive behavior. The sealant containing the polysulfide of Comparative Example B3 in contast, often shows partially adhesive behavior.