POLYMER DISPERSIONS SUITABLE FOR FABRIC CONDITIONING TREATMENT

Abstract

The present invention relates to a process for preparing a dispersion (D°), comprising: (E1) a polymerization performed M in an aqueous medium in the presence of: ° at least a pre-polymer (pO) of formula (R.sup.11)X—Z.sup.11—C(═S)—Z.sup.12-[A]-R.sup.12, which is soluble in the aqueous medium ° at least one free-radical polymerization initiator; and ° at least one ethylenically unsaturated hydrophobic monomer (m) with a ratio m/pO of the mass of the monomers (m) to the quantity of pre-polymer (pO) preferably below 10 000 g/mol whereby a dispersion of copolymers is obtained, including polymers with a living character; (E2) a conversion of the terminal groups of the copolymers that deprive the copolymers of their living character. The invention also relates to the use of dispersion (D°) for forming dispersions of hydrophobic polymers (Dp), suitable e.g. in fabric conditioning compositions.

Claims

1. A process for preparing a dispersion (D.sup.0), comprising the following successive steps: (E1) a free radical polymerization is performed in an aqueous medium (M) in the presence of: at least a pre-polymer (p0) soluble in the medium (M), having the following formula (I):
(R.sup.11).sub.x—Z.sup.11—C(═S)—Z.sup.12-[A]-R.sup.12  (I) wherein: Z.sup.11 represents C, N, O, S or P, Z12 represents S or P, R11 and R12, which may be identical or different, represent: an optionally substituted alkyl, acyl, aryl, alkene or alkyne group (i), or a saturated or unsaturated, optionally substituted or aromatic carbon-based ring (ii), or a saturated or unsaturated, optionally substituted heterocycle (iii), these groups and rings (i), (ii) and (iii) being optionally substituted with substituted phenyl groups, substituted aromatic groups or groups: alkoxycarbonyl or aryloxycarbonyl (—COOR), carboxyl (—COOH), acyloxy (—O.sub.2CR), carbamoyl (—CONR.sub.2), cyano (—CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimido, maleimido, succinimido, amidino, guanidimo, hydroxyl (—OH), amino (—NR.sub.2), halogen, allyl, epoxy, alkoxy (—OR), S-alkyl, S-aryl, groups of hydrophilic or ionic nature such as the alkali metal salts of carboxylic acids, the alkali metal salts of sulphonic acid, polyalkylene oxide (PEO or PPO) chains and cationic substituents (quaternary ammonium salts), R representing an alkyl or aryl group, x corresponds to the valency of Z.sup.11, or alternatively x is 0, in which case Z.sup.11 represents a phenyl, alkene or alkyne radical, optionally substituted with an optionally substituted alkyl; acyl; aryl; alkene or alkyne group; an optionally substituted, saturated, unsaturated, or aromatic, carbon-based ring; an optionally substituted, saturated or unsaturated heterocycle; alkoxycarbonyl or aryloxycarbonyl (—COOR); carboxyl (COOH); acyloxy (—O.sub.2CR); carbamoyl (—CONR.sub.2); cyano (—CN); alkylcarbonyl; alkylarylcarbonyl; arylcarbonyl; arylalkylcarbonyl; phthalimido; maleimido; succinimido; amidino; guanidimo; hydroxyl (—OH); amino (—NR.sub.2); halogen; allyl; epoxy; alkoxy (—OR), S-alkyl; S-aryl groups; groups of hydrophilic or ionic nature such as the alkali metal salts of carboxylic acids, the alkali metal salts of sulphonic acid, polyalkylene oxide (PEO or PPO) chains and cationic substituents (quaternary ammonium salts); and [A] represents a polymer chain; and at least one free-radical polymerization initiator; and at least one ethylenically unsaturated hydrophobic monomer (m) with a ratio m/p0 of the mass of the monomers (m) to the quantity of pre-polymer (p0) below 10 000 g/mol. whereby a dispersion of copolymers is obtained, including polymer chains having a (R.sup.11).sub.x—Z.sup.11—C(═S)—Z.sup.12— terminal group, that confer to these chains a living character; and then (E2) the (R.sup.11).sub.x—Z.sup.11—C(═S)—Z.sup.12— terminal groups present in the dispersion of copolymers as obtained in step (E1) are converted into other groups that deprive the copolymers of their living character.

2. The process according to claim 1, wherein the ratio m/p0 of the mass of the monomers (m) to the quantity of pre-polymer (p0) is between 5,000 and 10.000 g/mol.

3. The process according to claim 1, wherein the polymer chain [A] of the pre-polymer (p0) comprises: cationic monomers Ac, selected from the group consisting in: Trimethylammoniumpropylmethacrylamide; (3-methacrylamidopropyl)trimethylammonium; (3-acrylamidopropyl)trimethylammonium; Methacryloyloxyethyltrimethylammonium; acryloyloxyethyltrimethylammonium; methyldiethylammoniumethyl acrylate; benzyldimethylammoniumethyle acrylate; 1-ethyl 2-vinylpyridinium; 1-ethyl 4-vinylpyridinium; N-dimethyldiallylammonium; dimethylaminopropylmethacrylamide N-(3-chloro-2-hydroxypropyl)trimethylammonium chloride; and monomers of formula of ##STR00005## where each of X.sup.− is an anion, is chloride or methylsulfate; and non-ionic monomers An.

4. The process of claim 3, wherein the chain [A] is a statistical copolymer of acrylamide (AM) and (3-acrylamidopropyl)trimethylammonium chloride (APTAC).

5. The process according to claim 1, wherein the pre-polymer (p0) is obtained by a preparation step (E.sup.0) of controlled radical polymerization of a composition comprising: monomers containing identical or different hydrophilic monomers mAh as defined above, optionally together with at least one hydrophobic monomer mAH a radical polymerization control agent including a group (R.sup.11)x-Z.sup.11—C(═S)—Z.sup.2—, wherein R.sup.11, x, Z.sup.11, and Z.sup.12 are as defined in claim 1; and a free-radical polymerization initiator.

6. The process according to claim 5, wherein the monomers (m) comprise alkyl (meth)acrylates containing less than 30 carbon atoms.

7. The process according to claim 1, wherein step (E2) comprise the addition of a peroxide or peracid to the dispersion obtained in step (E1).

8. A dispersion (D.sup.0) obtainable according to the process of claim 1.

9. An aqueous medium comprising a dispersion (D.sup.0) according to claim 8 and hydrophobic monomers.

10. A process for preparing a dispersion (D) of hydrophobic monomers in an aqueous medium, comprising the preparation of a dispersion (D.sup.0) according to the process of claim 1 and then a step (E3) wherein said dispersion D.sup.0 is contacted with the hydrophobic monomers.

11. A dispersion (D) of hydrophobic monomers in an aqueous medium, obtainable according to the process of claim 10.

12. A process for preparing a dispersion (Dp) of hydrophobic polymer in an aqueous medium, that comprises a step (E4) wherein all of part of the hydrophobic monomers contained in a dispersion (D) according to claim 11 are polymerized.

13. A dispersion (Dp) of hydrophobic polymers in an aqueous medium obtainable according to the process of claim 12.

14. A fabric conditioning composition comprising the dispersion (D.sup.0) according to claim 8.

15. A fabric conditioning composition comprising the dispersion (Dp) according to claim 13.

16. The process according to claim 6, wherein the non-ionic monomers An are selected from (meth)acrylamides and derivatives or (meth)acrylic acids and derivatives

17. The process according to claim 6, wherein the monomers (m) comprise butyl acrylate and/or 2-ethylhexyl acrylate.

Description

EXAMPLES

Example 1

Preparation of a Pre-Polymers (Macro Transfer Agents) Useful According to the Invention

Example 1.1

Preparation of a pre-polymer composition MCTA 1

[0185] In a 2000 mL glass bottle were introduced: 441.7 g of 50% wt water solution of Acrylamide (AM) 105.7 g of a 75% wt water solution of (3-acrylamidopropyl)trimethylammonium chloride (APTAC); and 448.3 g of demineralized water. The pH (initially equal to 6.49) was then adjusted to pH=3.03, by addition of H.sub.2SO.sub.4 (10% wt water solution).

[0186] 12.5272 g of Rhodixan® A1 (Solvay) and 195.9 g of ethanol were then added, that turns the obtained mixture to be cloudy. After 10 min of strong agitation, 1.6254 g of V50 initiator were added.

[0187] The obtained mixture was introduced in a 2000 mL double-jacketed glass vessel equipped with an agitation anchor, a nitrogen inlet, a temperature sensor and a condensor.

[0188] Nitrogen was introduced (bubbling) during 30 min at room temperature (25° C.) and then the reaction medium was heated at 63° C. within 30 min. A marked exothermicity was observed around 50° C. The nitrogen was then used a nitrogen blanket and the temperature of 63° C. was maintained during 10 h.

[0189] The reaction medium was then cooled down to 23° C. within 30 min and let at room temperature overnight. A viscous liquid was then obtained, having a dry extract of 29.84%.

[0190] Ethanol and a part of the water were evaporated (rotavapor—55° C., 50 mbar), leading to a composition MCTA1, having a dry extract of 48.3% (measured with a thermobalance—1 h, 130° C.).

[0191] The awaited molar composition of the polymer (90/10 in mol for AM/APTAC) has been confirmed by RMN .sup.1H, that also indicates a Mn of about 6 700 g/mole.

Example 1.2

Preparation of a pre-polymer composition MCTA 2

[0192] In a 2000 mL double-jacketed glass vessel equipped with an agitation mobile, a nitrogen inlet, a temperature sensor and a condensor, 29.45 g of a 50% wt water solution of AM; 7.03 g of a 75% wt water solution of APTAC; and 248 g of demineralized water were introduced. The pH (initially equal to 3.66) was then adjusted to pH=2.92, by addition of H.sub.2SO.sub.4 (10% wt water solution). 41.66 g of Rhodixan® A1 (Solvay) and 166.63 g of ethanol were then added.

[0193] Nitrogen was introduced (bubbling) during 45 min at room temperature (25° C.) and then the reaction medium was heated at 63° C. within 60 min.

[0194] When the temperature has reached 63° C., 5.42 g of a 5% water solution of V50 was added and the following parallel injections were started: [0195] 1952.99 g of a first solution water solution of AM (50% in water—for a total of 1442.95 g) and APTAC (75% in water, for a total of 344.70 g) was continuously added within 240 minutes; [0196] 48.81 g of a second water solution of V50 (5% in water) was added within 240 minutes

[0197] The temperature of 63° C. was maintained during 8 h. A very marked exothermicity was observed. The reaction medium was cooled down to 20° C. within 60 min and let at this temperature overnight.

[0198] A liquid (=composition MCTA2) was then obtained, having the following features: [0199] Dry extract (thermobalance—120 min 130° C.): 44.00% [0200] M.sub.n=5300 g.Math.mol.sup.−1 (measured by RMN).

Example 2

Use of the Pre-Polymers of Example 1 for Preparing Dispersions (D0) According to the Invention

Example 2.1

Preparation of a Dispersion D0-1 from the Composition MCTA1 of Example 1.1

[0201] 192.8 g of the composition MCTA1 of example 1.1, 27.96 g of butyl acrylate (ABu), 414.3 g of demineralized water and 0.71 g of an aqueous solution of sodium persulfate (NaPS) having a NaPS concentration of 10% wt were mixed in a 600 mL glass beaker and then transferred in a 1000 mL double-jacketed glass vessel equipped with an lightning type agitation, a nitrogen inlet and a condensor.

[0202] Nitrogen was introduced (bubbling) during 1 h at room temperature (25° C.) and then the reaction medium was heated at 75° C. within 1 h. After 20 minutes of heating, 56.7 g of the composition MCTA1 of example 1.1 and 21.6 g of demineralized water were added to the reaction medium.

[0203] When the temperature has reached 75° C., 6.22 mL of a 10% wt water solution of NaPS are added from a syringe pump within 2 hours, and 162.46 mL d'ABu are added from a second syringe pump within 2.5 hours.

[0204] At the end of the injections, the reaction medium is let during 2 hours at 75° C. and then cooled down overnight.

[0205] The glass vessel is unloaded and an homogeneous white latex having a pH of about 3-4 is obtained, referred herein as D0-1-Xa, without any crusts visible on the stirring blade.

[0206] 517.9 g of the obtained D0-1-Xa latex are re-introduced in the glass vessel and then heated to 70° C. within 1 h, and then 9.68 g of peracetic acid (35% wt aqueous solution) are added within 1 h. The reaction medium is let 1 h at 70° C. after the end of the addition of the peracetic acid.

[0207] A white latex is then obtained, referred herein as D0-1, having the same visual appearance as D0-1-Xa.

[0208] UV analysis indicates that a complete dexanthatation occurred. And a light scattering measure confirms that the particle size is unchanged in comparison to D0-1-Xa.

[0209] The latex D0-1 exhibits the following features: [0210] Dry extract (thermobalance—150 min 130° C.): 33.54% [0211] Average particle size (SLS—Nanosizer malvern): 252.5 nm

Example 2.2

Preparation of a Dispersion D0-2 from the Composition MCTA2 of Example 1.2

[0212] 675.7 g of the composition MCTA2 of example 1.2, 41.92 g of butyl acrylate (ABu), 685 g of demineralized water and 1.03 g of an aqueous solution of sodium persulfate (NaPS) having a NaPS concentration of 10% wt were introduced in a 2000 mL double-jacketed glass vessel equipped with an agitation mobile, a nitrogen inlet, a temperature sensor and a condensor.

[0213] Nitrogen was introduced (bubbling) during 1 h at room temperature (25° C.) and then the reaction medium was heated at 75° C. within 1 h.

[0214] When the temperature has reached 75° C., 9.345 g of a 10% wt water solution of NaPS are added from a syringe pump within 2.5 hours, and 237.56 g of ABu are added from a second syringe pump within 2 hours.

[0215] At the end of the injections, the reaction medium is let during 2 hours at 75° C. and then cooled down overnight.

[0216] The glass vessel is unloaded and an homogeneous white latex having a pH of about 3-4 is obtained, referred herein as D0-2-Xa.

[0217] 1621.97 g of the obtained D0-2-Xa are re-introduced in the glass vessel and then heated to 70° C. within 1 h, and then 35.98 g of peracetic acid (35% wt aqueous solution) are added within 1 h The reaction medium is let 1 h at 70° C. after the end of the addition of the peracetic acid.

[0218] A white latex is then obtained, referred herein as D0-2, having the same visual appearance as D0-2-Xa.

[0219] This latex D0-2 exhibits the following features: [0220] Dry extract (thermobalance—75 min 115° C.): 35.38% [0221] Average particle size (SLS—Nanosizer malvern): 95.42 nm (PDI=0.094)

Example 3

Use of the Dispersions of Example 2 for Preparing Dispersions of Polymers (Dp) According to the Invention

Example 3.1

Preparation of a Dispersion Dp-1 (Latex) from the Dispersion D0-1 of Example 2.1

[0222] 78.5 g of the dispersion D0-1 of example 2.1 and 191 g of demineralized water were mixed in a 600 mL glass beaker and then transferred in a in a 500 mL double-jacketed glass vessel equipped with an lightning type agitation, a nitrogen inlet and a condenser Nitrogen was introduced (bubbling) during 1 h at room temperature (25° C.) and then the reaction medium was heated at 70° C. within 1 h.

[0223] When the temperature has reached 70° C., 2.8970 g of a 10% wt water solution of NaPS and 86.406 mL of ABu are added from a syringe pump within 4 hours. The reaction medium is then cured 2 h at 70° C. after the end of the addition.

[0224] An homogeneous latex Dp-1 is then obtained, having the following features: [0225] Dry extract (thermobalance—60 min, 130° C.): 30.03% [0226] Average particle size (SLS—Nanosizer malvern): 172.8 nm [0227] Residual ABu (gas chromatography): 610 ppm

Example 3.2

Preparation of a Dispersion Dp-2 (Latex) from the Dispersion D0-2 of Example 2.2

[0228] 252.65 g of the dispersion D0-2 of example 2., 530.52 g of demineralized water and 3.36 g of tert-dodecylmercaptan (TDM) were introduced in a 2000 mL double-jacketed glass vessel equipped with an agitation mobile, a nitrogen inlet, a temperature sensor and a condensor.

[0229] Nitrogen was introduced (bubbling) during 1 h at room temperature (25° C.) and then the reaction medium was heated at 70° C. within 1 h.

[0230] When the temperature has reached 70° C., 7.78 g of a 10% wt water solution of NaPS was added as a shot and then 209.28 g of ABu were added within 4 hours. The reaction medium is then cured 2 h at 70° C. after the end of the addition of ABu.

[0231] An homogeneous latex Dp-2 is then obtained, having the following features: [0232] Dry extract (thermobalance—60 min, 130° C.): 30.3% [0233] Average particle size (SLS—Nanosizer malvern): 93.31 nm (PDI=0.101) [0234] Residual ABu (gas chromatography): 1221 ppm

Example 3.3

Preparation of a Dispersion Dp-3 (Latex) from the Dispersion D0-2 of Example 2.2

[0235] 252.65 g of the dispersion D0-2 of example 2., 517.30 g of demineralized water and 16.80 g of TDM were introduced in a 2000 mL double-jacketed glass vessel equipped with an agitation mobile, a nitrogen inlet, a temperature sensor and a condensor.

[0236] Nitrogen was introduced (bubbling) during 1 h at room temperature (25° C.) and then the reaction medium was heated at 70° C. within 1 h.

[0237] When the temperature has reached 70° C., 7.78 g of a 10% wt water solution of NaPS was added as a shot and then 209.28 g of ABu were added within 4 hours. The reaction medium is then cured 2 h at 70° C. after the end of the addition of ABu.

[0238] An homogeneous latex Dp-3 is then obtained, having the following features: [0239] Dry extract (thermobalance—60 min, 130° C.): 32.30% Average particle size (SLS—Nanosizer malvern): 94.22 nm (PDI=0.077) [0240] Residual ABu (gas chromatography): 1005 ppm

Example 4

Use of the Dispersions Dp-1, Dp-2 and Dp-3 of Example 3 for a Fabric Treatment

[0241] The dispersions of latex as obtained in Example 3 were used for a fabric treatment.

[0242] Each of the dispersions Dp-1, Dp-2 and Dp-3 of example 3 was first diluted with water to a concentration of 0.2 wt. %, and then left for 12 hours at 25° C. Then, each of the obtained diluted dispersions was again diluted down with water to a concentration of 0.004 wt. % for the fabric treatment, thus leading to three fabric treatment compositions referred as C1, C2 and C3 (C1 correspond to the twice diluted dispersion Dp-1, C2 correspond to the twice diluted dispersion Dp-2, and C3 correspond to the twice diluted dispersion Dp-3).

[0243] The composition were used for treating 40 g Fabric (with 1000 ml of composition) in the conditions described herein-after.

[0244] For sake of comparison, the softening performance of the compositions C1, C2 and C3 were compared to a positive Benchmark (PBM) and to a negative benchmark (NBM), defined herein-after, used in the same conditions.

4.1. Materials

4.1.1 The Treated Fabrics

[0245] Cotton terry towels with approximate size 20×20 cm were used

4.1.2. The Positive Benchmark PBM (Comparative)

[0246] A fabric treatment composition was used as a positive benchmark containing the commercially available quat Fentacare® TEP-88 of formula:

##STR00004##

at the same weight concentration as in the compositions C1, C2 and C3.

4.1.3. The Negative Benchmark NBM (Comparative)

[0247] Pure water (without any additive) was used as the negative Benchmark

4.2. Fabric Treatment

[0248] The fabrics were treated in a two-part procedure

[0249] (A) Treatment with the Tested Composition (C1, C2, C3, PBM or NBM). [0250] 1) 3 pieces of fabric with approximate weight of ˜ 40 grams were put into the vessel of a tergotometer. If the weight of the fabrics does not add up to 40 g an additional small piece is added in order for the total weight of the fabrics to be 40 g. This additional piece is not used in the softness evaluation. [0251] 2) 1000 ml of the tested composition (C1, C2, C3, PBM or NBM) were added [0252] 3) The fabrics were soaked for 10 minutes at speed of rotation of the tergotometer of 75 rpm at temperature of 25±1° C.

[0253] (B) Drying and Conditioning. [0254] 1) The fabrics as obtained at the end of step (A) are spin-dried for 10 minutes at 720 rpm in spin-dryer (Samsung Washing Machine, Model No: WA90F5S9). [0255] 2) The fabrics are hanged on a clothes rack in a special room (humidity: 60±5%; temperature: 20±1° C.). The fabrics are well-separated (at least one bar distance) from each other in order to avoid contamination.

4.3. Softness Assessment

[0256] The softness was assessed in a panel of 6 people. The panellists assign a number from 1 to 5 characterizing the softness, higher score corresponds to better softness.

[0257] The panels included 4 samples: [0258] (1) One sample of fabrics treated with the Negative benchmark (NBM), namely with no softening formulation added (only treated with water). The typical softness score assigned to the negative benchmark is in the range of ≈2.4÷2.6. [0259] (2) One sample of fabrics treated with the Positive benchmark (PBM). The score of positive benchmark is in the range ≈3.6÷3.9 [0260] (3) 2 sample of fabrics treated with one of composition C1, C2 or C3.

[0261] Each fabric is touched only 3 times. The number of touches has to be limited as touching the fabric can lead to increase in softness. We have a total of 18 determinations of the softness for each system. The softness is calculated as an average of the 18 values. The standard deviation of the measurement is calculated in the following manner

[00001]$S{D}_P=\sqrt{\frac{\left(n_1-1\right)S{D}_1^2+\left(n_2-1\right)S{D}_2^2+.Math.+\left(n_k-1\right)S{D}_k^2}{n_1+n_2+.Math.+n_k-k}}$

[0262] Here SD.sub.P is the so-called pooled standard deviation; SD.sub.1, SD.sub.2, SD.sub.K are the standard deviations for each group; n.sub.1, n.sub.2, n.sub.k are the number of fabrics in each group. In our case we have 3 groups each containing the same number of fabrics (6). SD.sub.1, SD.sub.2 and SD.sub.3 are the standard deviations of the determination of the score from the 1.sup.st, 2.sup.nd and 3.sup.rd touch, respectively. The above equation can be written as follows:

[00002]$S{D}_P=\sqrt{\frac{S{D}_1^2+S{D}_2^2+S{D}_3^2}{3}}$

[0263] The standard error for each system is calculated via the following equation:

[00003]$S{E}_P=\frac{S{D}_P}{\sqrt{N}}$

[0264] Here N=18 is the total number of the measurements (or touches here).

[0265] The softness score assigned to a studied sample is not an absolute value, and makes sense only when compared to the values of the positive and negative benchmark. However the values of the softness score of the PBM and NBM vary in a certain range. Therefore a direct comparison between the softness scores of samples studied in different panels is misleading. A correct comparison would reflect the degree in which the compared samples differ from the PBM and the NBM. In order to be able to compare systems studied in different panels we introduced a parameter called softness degree, SDG:

[00004]$\mathrm{SDG}=\frac{\mathrm{Score}\left(\mathrm{studied}\mathrm{system}\right)-\mathrm{Score}\left(\mathrm{NBM}\right)}{\mathrm{Score}\left(\mathrm{PBM}\right)-\mathrm{Score}\left(\mathrm{NBM}\right)}\times 100$

[0266] The SDG is measured in percent. The NBM and PBM have 0% and 100% SDG, respectively. The majority of the studied systems have SDG in the range 0÷100%, some exceptionally well performing systems have SDG>100%.

[0267] The standard error of the softness degree is calculated via the standard rules for error propagation:

Δ(a±b)=√{square root over (Δa.sup.2+Δb.sup.2)}

Δ(a/b)=(a/b)√{square root over ((Δa/a).sup.2+(Δb/b).sup.2)}

[0268] Softness degree of the studied latexes at the working concentration (1×C.sub.W).

TABLE-US-00001 Used composition Softness degree, SE.sub.P C1 58% 14%  C1 64% 7% C1 69% 5%