CN1217006A - Color stabilization of aqueous heterocyclic copolymer - Google Patents
Color stabilization of aqueous heterocyclic copolymer Download PDFInfo
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- CN1217006A CN1217006A CN 95196697 CN95196697A CN1217006A CN 1217006 A CN1217006 A CN 1217006A CN 95196697 CN95196697 CN 95196697 CN 95196697 A CN95196697 A CN 95196697A CN 1217006 A CN1217006 A CN 1217006A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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Abstract
This invention relates to a process for the production of substantially odorless, color stable N-vinyl heterocyclic copolymer which includes contacting alcohol solution of the copolymer, under reduced pressure, with water and a reducing agent selected from the group of a nitrogen containing borane complex, sulfurous acid and an alkali metal salt of sulfurous acid and recovering an aqueous, 10-80 wt.% solids solution of the copolymer having a substantially color free stability for a period of more than a year. The invention also relates to an N-vinyl heterocyclic copolymer in substantially pure deionized water or in aqueous alcoholic solution which exhibits significantly reduced color and odor and which is obtained by contacting an alcohol-copolymer mixture with water and a nitrogen containing, trivalent boron complex compound and stripping alcohol from the resulting mixture.
Description
Background of the present invention
N-vinyl lactam polymkeric substance is important component in the responsive system of many colors, and this comprises their resins as the fabric spinning, the milk sap of cloth print slurry, and the direct additive of dyestuff and other use the application of high processing temperature.These polymkeric substance also are used in makeup and the medicine field, but the smell that manifests and dislike of its color is unhappy.A main drawback that uses this lactan and other N-vinyl heterocycle multipolymer be them leave standstill or heat-processed in quick yellowing of trend or blackout, no matter whether the alcoholic solution of the heterocycle vinyl monomer when adding polymerization reactor or the corresponding copolymerization product of acquisition is colourless at first, this problem exists equally.Therefore think that chromophoric group or other color introduced with heterocyclic monomer form impurity formation and rotten rapidly in the process of leaving standstill to some extent in polymerization process.
In the exchange of solvent process, before or after with various stablizers, as ion exchange resin, absorption agent and/or oxygenant add that entry or alcohol solution overcome or the various proposals that improve this problem have been proved unsatisfactory and can not reach secular water-white colour stability.In fact, randomly several stablizers that use with auxiliary can make the finished product have offensive odour in addition or itself have corrodibility owing to acid ph value is lower than 4.0, so just caused new problem, improved expense and/or limited the concentration of multipolymer in many prescriptions.
Therefore, an object of the present invention is to overcome N-vinyl heterocycle solution, especially the problems referred to above of N-vinyl lactam aqueous copolymers solution and shortcoming.
Another object of the present invention provides a kind of colour stable of the N-vinyl heterocycle multipolymer that decolours, tasteless solution of being easy to usually, and provide a kind of have extended storage stability and and makeup, the aqueous solution of the described multipolymer of the component compatibility in medicine and other prescription.
A further object of the present invention is to provide above-mentioned advantage by viable commercial and economically feasible method.
Will and disclosing from following description with many other advantages, of the present invention these embody.
The present invention
By the present invention, a kind of deionized water of the N-vinyl heterocycle multipolymer for preparing colour stable or the method for alcohol solution are provided, this method is the about 5 weight % of about 0.02-with the alcoholic solution of multipolymer and multipolymer weight, is the stablizer of the about 2 weight % of about 0.02-or reductive agent contact preferably.Stablizer of the present invention is selected from the borane title complex, an alkali metal salt of sulfurous acid or sulfurous acid and composition thereof, and the mixture of gained removed alcoholic solvent through vacuum distilling.
Same by the present invention, a kind of water or alcohol solution of colour stable are provided, it comprises (a) deionized water, (b) account for total solution weight the about 70 weight % of about 10-N-vinyl heterocycle multipolymer and (c) concentration be the nitrogenous trivalent boron complexes of the about 2 weight % of about 0.02-of multipolymer weight.
In this manual, " low alkyl group " is meant C
1-C
4Alkyl.
Borane title complex of the present invention comprises organic or inorganic nitrogen-containing compound, as borane ammonia (BH
3-NH
3); Randomly by rudimentary (C
1-C
4) the morpholine borane that replaces of alkyl, for example 4-ethyl morpholine borane; Borane C
1-C
4Alkylamine, for example borane TERTIARY BUTYL AMINE ([CH
3]
3C-NH
2-BH
3), the borane Trimethylamine 99; Octahydro three boric acid tetramethyl-ammoniums and siliceous borane, for example amino borane (SiH of silyl
3-BH
2-NH
3).Suitable alkali sulfite metal-salt comprises S-WAT and/or potassium or sodium bisulfite and/or potassium.Stablizer of the present invention contacted with copolymer solution before the generation variable color, that is multipolymer has just reclaimed from polymerization reactor afterwards and has comprised that being used for partly or entirely steaming the alcohol that removes copolymer solution carries out before any operation generation of exchange of solvent with deionized water.Observe that in time to add the stablizer this point be vital for obtaining storage period greater than the stable colourless basically copolymer solution in 1 year, reason is to find concerning the polymers soln of yellowing or blackout, the effect of reductive agent of the present invention mainly is to form inhibitor as color, but not the SYNTHETIC OPTICAL WHITNER or the agent of losing lustre.In the aforementioned stable agent, from the viewpoint of expense and being easy to get property, stablizer is the borane low-grade alkylamine preferably, as the borane TERTIARY BUTYL AMINE, and sodium bisulfite.
When selecting borane/amine complex as stablizer, the initial ammonia that discharges can send undesirable smell and produce and compare higher pH.Yet when this stablizer adds fashionablely with the solution form of the 0.005-1.0 weight % weak organic acid (for example acetate) that contains the borane total solution weight, these effects are reduced to acceptable scope.
With deionized water generation exchange of solvent before, add to such an extent that the copolymer solution of autoreactor or the concentration that adds the stablizer in the multipolymer alcoholic solution are the about 0.2 weight % of about 0.05-preferably, also can use although be below or above the interior amount of above-mentioned scope.
N-vinyl heterocyclic monomers of the present invention is those monomers that contain 3-6 ring carbon atom, comprise the N-vinyl pyrrolidone, the N-vinyl imidazole, N-vinyl morpholine, N-vinyl pyridine and N-caprolactam, each in them all can randomly be replaced by low alkyl group on carbon atom of N-heterocyclic.The comonomer that multipolymer of the present invention is suitable is the lower acid vinyl ester, vinyl-acetic ester for example, propionate, vinyl butyrate, methyl acrylate, ethyl propenoate; Vinyl cyanide; Vinylbenzene and their mixture.
Multipolymer of the present invention is that those contain the multipolymer that the about 80 weight %N-vinyl heterocyclic monomers of about 40-and the about 60 weight % of about 20-have the copolymerizable vinyl monomer of random, grafting, line style or branched structure ideally.These multipolymers are further characterized in that the K value is about 100 for about 10-, and being equivalent to number-average molecular weight is about 500-about 300,000.The K value of multipolymer is preferably about 20-50, and molecular weight is about 10,000-100,000.Equally, the present invention preferably the multipolymer kind be that weight ratio is that about 50-80 part lactan (for example VP) is than N-vinyl pyrrolidone/vinyl-acetic ester (VP/VA) multipolymer of 50-20 part as vinyl-acetic ester (VA) and so on comonomer; Most the weight ratio of wishing is 55-70 part VP and 45-30 part VA, and these multipolymer kinds are the multipolymer that needs most of colour stable seemingly.
The solid solution of the 10-80 weight % that multipolymer of the present invention is normally reclaimed from the solution polymerization that free radical causes wherein uses low-level chain triacontanol, particularly ethanol, and the Virahol and/or the trimethyl carbinol are as solvent medium.Although this is useful in many commodity are used for multipolymer/alcoholic solution, for example be used in tackiness agent, the agent (grooming agents) of comb dress is as hair spray, curly hair water, shampoo paste, toning agent, dyestuff and purificant, the photosensitive film protective agent, the plant sprays, in footwear and furniture polish and the decoration sprays, but a large amount of human consumers still needs aqueous copolymers solution.In this exchange of solvent stage, have maximum variable color potentiality, and subsequently leave standstill or storage process in take place continuously and cumulative yellowing and blackout.Also can observe the yellowing of multipolymer alcoholic solution, but its degree is littler than aqueous copolymers solution.To multipolymer of the present invention stable in deionized water, the demand of water-white solution had become the theme of many tests already; Yet do not have in the existing stabilising method a kind ofly can prepare all satisfactory in all respects or showed 1 year or the solution of permanent stability more for many years.Find now in the solvent exchange operation process, must keep and some relevant critical machined parameters of stablizer contact in order to obtain very gratifying product.Have only these indexs of abideing by, could obtain the aqueous copolymers solution that has color and smell stability concurrently of the present invention.
More specifically, aqueous copolymers solution of the present invention can prepare like this, promptly reclaiming 10-80 weight % from the zone of convergency, add stablizer when being dissolved in pure copolymerization solid for 50-70 weight % preferably immediately, perhaps when needs carry out exchange of solvent with water, before steaming except that operation, alcohol adds stablizer.Before removing, steaming stablizer can be added in deionized water charging or the alcoholic solvent/copolymer mixture.In addition, it is important steaming divided by carrying out exchange of solvent by alcohol in the vacuum at a lower temperature, promptly is being lower than the temperature of the about 20-740mmHg of bar absolute pressure and about 35-85 ℃, is preferably to be lower than about 20-120mmHg of bar absolute pressure and about 40-65 ℃ temperature.
With the exchange of solvent of water can below dual mode carry out (a) single stepping that carries out with the water of about 100-150 volume % of the alcohol that exists in the copolymer mixture, or the operation of (b) carrying out stage by stage with the water of the pure about 150 volume % of about 50-.In the later case, all the stablizer of amount can add first steaming except that in the stage, and perhaps the increment of required total amount can remove in the stage in several steamings and add.The water that adds between the vacuum distilling stage can be same amount, and perhaps steaming to remove at subsequently alcohol increases in the step or reduce.Because from steaming the alcohol that removes recovery the section (one or more) is purified basically, so it can be used as the monomeric solvent recycled of raw feed to polymerization reactor; Like this, the operate continuously mode that this process can less expensive is carried out, and also can carry out when needs simultaneously in batches.The most advantageously, carry out under the situation of the deionized water that the volume of this process alcohol that can exist in pure recirculation adds volume and the copolymer solution of handling when steam removing is identical or identical haply.Used deionized water is a high purity in exchange, for example the water that obtains through deionization in mould, organism and dust can't the closed systems of pollution products.Following under the above-mentioned condition, obtaining when 10 weight % solids concns APHA color permanent stability less than 10 VP/VA aqueous copolymers solution.Other N-vinyl heterocycle multipolymer of the present invention can reach similar color and smell stability.If need further processing, the aqueous solution of multipolymer can be carried out drying, obtain to be suitable for being squeezed into the colourless resin of stablizing of long filament.
At room temperature use Klatt (Klett) groove of 20 * 80mm, the colour stability that (Hunter) colorimeter in the Hunter (model is D25P-9) is gone up the VP/VA solution of measuring of the present invention (50% solid) did not demonstrate variable color in 13 months.
In the copolymer solution except comprising stablizer, in final copolymer solution, can also comprise the about 2 weight % of about 0.05-, be more generally as the buffer reagent of the about 0.4 weight % of about 0.1-, for example alkali-metal acetate, carbonate, supercarbonate, or phosphoric acid one or disodium or potassium, to guarantee that required pH is in the scope of 4-7.Other additive also can randomly use in the aqueous solution of polymer product, and it comprises the sanitas that reaches 5 weight %, as GERMALL
, GLYDANT
And other.
At describe, in general terms after the present invention, referring now to following embodiment embodiment preferably is described, but should not be counted as to above-mentioned definition broad with appended claims in the restriction of the scope of the invention.
Embodiment 1
Preparation contains the colourless solution of 100g Virahol and 100g N-vinyl-2-Pyrrolidone/vinyl acetate copolymer (70: 30 weight parts).Solution is put into rotatory evaporator, and Virahol is substituted by water therein.In vaporizer, add the 100g deionized water.Then with gained solution under 40 ℃ of about 25mmHg through vacuum distilling 35 minutes, the liquid of about 100g is removed as distillate in this process.Then in vaporizer, add the 100g deionized water again, remove the 100g distillate again.To contain the 100g multipolymer, 100g water and be chilled to room temperature less than the obtained aqueous solution of 0.2g Virahol reclaims the product of this law of colorless and odorless.This product is divided into the sample of two 100g, A and B.In sample A, add 0.2g borane-Trimethylamine 99 title complex immediately, and sample B disregards.Then two samples are placed in 50 ℃ the baking oven 10 months, subsequently they are observed.See that the sample A that handled with borane-Trimethylamine 99 title complex is colourless, its APHA color is 55.1.On the contrary, untreated sample B demonstrates deep yellow color, and the APHA observed value is 1,000.
Embodiment 2
Under 85 ℃, at 0.6g 2, two (2-methylbutyronitrile) initiators of 2-azo exist down, make VP and VA carry out solution polymerization under nitrogen purge, obtain the 50 weight % solid solutions that 100g VP/VA (70: 30) is dissolved in the 100g Virahol.This solution is divided into respectively is two samples (C-D) of 100g.
After the polymerization fully, in sample C, add 0.2g borane-TERTIARY BUTYL AMINE title complex immediately; And sample D handles without stablizer.The APHA color of measure sample C and D after polymerization one finishes and at room temperature stores 12 months again.The results are shown among the table 1A.
Repeat embodiment again 2 four times except replacing borane-Trimethylamine 99 title complex with the following stabilizers title complex:
Stablizer title complex sample
Borane-ammonia E and F
Borane-morpholine G and H
Octahydro three boric acid tetramethyl-ammonium I and J
Borane-4-ethyl morpholine K and L
The APHA color of these samples is listed among the table 1A equally.
Embodiment 3
The 50% solid polymer aqueous isopropanol that embodiment 2 is made is divided into two and respectively is the sample of 100g (M and N).As mentioned above, in a sample, add 0.2g borane-TERTIARY BUTYL AMINE after the polymerization fully immediately, and second sample disregarded.In the time of 40 ℃, use 50g water under the 20mmHg in rotatory evaporator then, steaming removes Virahol, reaches with purified deionized water (containing less than 0.001% organism) to make two samples carry out exchange of solvent.After finishing exchange of solvent and at room temperature storing 12 months again, measure the APHA color of these moisture copolymer sample M and N immediately.These the results are shown among the table 1B.
Except replacing borane-Trimethylamine 99, repeat embodiment again 3 four times with other boron complexes (be aforesaid those).
Stablizer title complex sample
Borane-ammonia O and P
Borane-morpholine Q and R
Octahydro three boric acid tetramethyl-ammonium S and T
Borane 4-ethyl morpholine U and V
The APHA color of these samples is listed among the table 1B equally.
Embodiment 4
Temperature rises to 23 ℃ from 16 ℃ under 10mmHg, makes the 250g that is dissolved in the 250g Virahol that obtains through solution polymerization under 85 ℃ 70: 30 VP/VA multipolymer (50% solid) carry out stage by stage deionized water solvent exchange.In rotatory evaporator, repeat twice of exchange of solvent.Each 250g water that adds when distillation finishes, boils off 250g liquid during beginning.Add before the entry for the first time, 0.50g (0.2% multipolymer) borane-TERTIARY BUTYL AMINE title complex is soluble in water and as colour stabilizer.Do not add stablizer second exchange of solvent stage.
After at room temperature storing 6 months, contain 50% multipolymer and be colourless and tasteless (APHA color originally is 18.0, and final APHA color is 10.2) less than the aqueous solution (100g) of the aforementioned stable of 0.1% Virahol.
With just yellowing significantly in the several hrs of similar copolymer sample after exchange of solvent is finished of stable complex processing, APHA originally is not 74.8.After at room temperature storing 6 months, yellow adds that to be deep to APHA color be 145.
The APHA color of table 1A VP/VA (70: 30) multipolymer aqueous isopropanol (50% solid)
*Add 0.02g acetate to prevent ammonia odor and control pH value
| Sample | ????F | ????E | ????D | ????C | ????H | ????G |
| Borane-amine complex * | Borane-TERTIARY BUTYL AMINE title complex | Borane-morpholine title complex | ||||
| No borane | 0.2g borane | No borane | 0.2g borane | No borane | 0.1g borane | |
| Originally APHA | 42.9 | ?9.6 | 46 | 16.2 | ????14.3 | 36.3 |
| APHA after 1 year | 105 | ?10.2 | 75.5 | 26.4 | ????61.4 | 38.6 |
| Sample | ????J | ????I | ????L | ????K |
| Octahydro three boric acid tetramethyl-ammoniums | Borane-4-ethyl morpholine title complex | |||
| No borane | 0.1g borane | No borane | 0.1g borane | |
| Originally APHA | 97.2 | 13.8 | 13.5 | |
| APHA after 1 year | 117 | 17.1 | 71.3 | 52.2 |
The APHA color of table 1BVP/VA (70: 30) aqueous copolymers solution (50% solid)
*Add 0.02g acetate to prevent ammonia odor and control pH value
| Sample | ????P | ????O | ????N | ?M | ????R | ????Q |
| Borane-amine complex * | Borane-TERTIARY BUTYL AMINE title complex | Borane-morpholine title complex | ||||
| No borane | 0.1g borane | No borane | 0.1g borane | No borane | 0.1g borane | |
| Originally APHA | ????245 | 9.0 | 211 | 17.5 | 200 | 50.1 |
| APHA after 1 year | ????414 | 11.7 | 228 | 14.3 | 242 | 32.1 |
| Sample | ????T | ????S | ????U | ????V |
| Octahydro three boric acid tetramethyl-ammoniums | Borane-4-ethyl morpholine title complex | |||
| No borane | 0.1g borane | No borane | 0.05g borane | |
| Originally APHA | ????195 | ????19.3 | ????236 | ????43.2 |
| APHA after 1 year | ????291 | ????3.4 | ????292 | ????73.5 |
Embodiment 5
Under 85 ℃, at 0.6g 2, two (2-methylbutyronitrile) initiators of 2-azo exist down, make VP and VA obtain the 50 weight % solid solutions that 100g N-vinyl pyrrolidone/vinyl-acetic ester (VP/VA 70: 30) is dissolved in the 100g Virahol through solution polymerization under nitrogen purge.This solution is divided into respectively is two samples of 100g (sample A and sample B).
After the polymerization fully, in sample A, add 0.2g borane-TERTIARY BUTYL AMINE title complex immediately; And sample B handles without stablizer.
In the time of 40 ℃, use 50g water under the 20mmHg in rotatory evaporator then, steaming removes Virahol, reaches with purified deionized water (containing less than 0.001% organism) to make two samples carry out exchange of solvent.Immediately after finishing exchange of solvent and at room temperature store the APHA color of measuring these moisture copolymer sample A and B after 12 months again.With APHA is that 211 sample B compares, and the initial APHA of sample A is 17.5.After 12 months, the APHA of sample A is 14.5, and the APHA of sample B is 228.
Embodiment 6
Under 23-30mmHg pressure and 28-33 ℃ of temperature, the solution (containing 50% solid) that colourless 70: 30 VP/VA multipolymers of new system are dissolved in the Virahol carries out deionized water solvent exchange stage by stage, the solution that described multipolymer is dissolved in the Virahol is 2 in the nitrogen purge system, under about 85 ℃, VP and VA obtained through solution polymerization under two (2-methylbutyronitrile) (Vazo 67 initiators) of 2 '-azo (its amount is 0.3% of product) existed.In rotatory evaporator, repeat twice of exchange of solvent.Before distillation for the first time, will account for multipolymer 0.24%, be dissolved in the 50g deionized water as the 0.12g sodium acetate of buffer reagent with as the 0.2g sodium bisulfite of colour stabilizer (account for multipolymer 0.4%).The volume of the Virahol that the volume of water and copolymer solution are used is identical.The water and the 100g multipolymer aqueous isopropanol that will contain sodium acetate and sodium bisulfite add in the rotatory evaporator.The distillation of fs continues 50 minutes, boils off about 50g liquid.In rotatory evaporator, add other 50g deionized water then again, wherein do not have buffer reagent or stablizer and exist, carry out the subordinate phase exchange of solvent, boil off 50g liquid again.Be recovered to and contain the 50g multipolymer, 50g water and less than the obtained aqueous solution of 0.1g Virahol.
It is colourless and tasteless (final APHA color is 38.0) basically that the aqueous solution of aforementioned stable was at room temperature stored after 6 months.
Obviously yellowing in the similar copolymer sample of as the sodium acetate of buffer reagent but not handling with stable complex that contains same ratio several hours after finishing exchange of solvent.After at room temperature storing 6 months, yellow has become scarlet, and APHA color is 117.Like this, obviously add in aqueous copolymers solution that to be low to moderate 0.4% sodium bisulfite (content with multipolymer is benchmark) be effective to the formation of inhibition color in long-time.
Embodiment 7
Except the exchange of solvent temperature is 46-50 ℃, pressure is outside the 25mm, and all the other all repeat the process of embodiment 5.Do not add sodium acetate as buffer reagent.After at room temperature storing 12 months, be deep yellow without the aqueous copolymers solution of stablizing, its APHA color is 290; And be water white with sodium bisulfite (0.2%, be benchmark in the weight that contains 50% solid copolymer solution) solution stable, that have tart flavour, its APHA color is 18.7.
Embodiment 8
In the exchange of solvent process that contains 50% solid VP/VA (70: 30) multipolymer at 100g, in deionized water, add outside 0.2g S-WAT (as colour stabilizer) and the 0.08g acetate (regulating the pH value), repeat the process of embodiment 5.After at room temperature storing 11 months, the solution of stablizing is very light yellow (APHA color is 76.6).The prepared aqueous copolymers solution of not stablizing is at room temperature stored after 11 months and is deep yellow simultaneously, and its APHA color is 387.
Embodiment 9
In the exchange of solvent process that contains 50% solid VP/VA (70: 30) multipolymer at 100g, in water, add 0.5g sulfurous acid (H
2SO
3, as colour stabilizer) and 0.12g sodium acetate (as buffer reagent) outside, repeat the process of embodiment 5.It is colourless after 6 months that the solution of stablizing is at room temperature stored, slightly little Huang (APHA color is 61.0).The aqueous copolymers solution of not stablizing that makes simultaneously and contain same ratio sodium acetate is at room temperature stored and is deep yellow (APHA color is 235) after 6 months.
Claims (26)
1. moisture in preparation, in the method for the 10-80% solid solution of colour stable, described solid solution is the copolymerizable vinyl comonomer that makes N-vinyl heterocyclic monomers that the about 80 weight % of about 40-contain 3-6 ring carbon atom and the about 20 weight % of about 60-through the polymerization acquisition, described method is included in the alcoholic solvent medium, in the presence of radical initiator, make above-mentioned monomer and comonomer carry out copolymerization, the K value that is created in the alcohol is the corresponding copolymers of about 10-about 100, make the alcohol copolymer mixture and the deionized water of gained carry out exchange of solvent, the improvements of this method comprise:
(a) make deionized water and the about 5 weight % of (2) about 0.02-of the about 150 volume % of the every volume about 50-of alcohol in described alcohol copolymer mixture and (1) be selected from sulfurous acid, alkali-metal sulphite or hydrosulphite, the stablizer of nitrogenous borane title complex and composition thereof contacts
(b) in the vacuum of the about 740mmHg of about 10-, be lower than under 90 ℃ the temperature, the alcohol/multipolymer/deionized water and the stablizer of gained distilled, with in exchanging, remove selectively with deionized water described alcohol and
(c) reclaim the aqueous solution contain the described multipolymer of 10-80% solid, this solution is stable in year at least and can prevents yellowing and blackout.
2. the method for claim 1, wherein alcohol is operated stage by stage with the described distillation of deionized water solution, repeating step (a) and (b) wherein, the fs distillation that step (b) representative is carried out under 20-120mmHg pressure, then the described stablizer of the about 2 weight % of about 0-do not exist or in the presence of carry out one and go on foot or the multistep distillation stage subsequently, as replenishing of 0.02-2 weight % described in the step (a) amount stablizer, more carry out pure distillation under the high vacuum and under the lower temperature at about 50-250mmHg.
3. method as claimed in claim 1 or 2, wherein at least a deionized water retort solution comprises the buffer reagent of the about 0.5 weight % of about 0.01-, so that the pH value is maintained at about 4-8.
4. method as claimed in claim 2, wherein multiple step (a) is to carry out under the identical haply situation of the volume of the alcohol that keeps in the volume of deionized water and system.
5. method as claimed in claim 3, wherein said buffer reagent are sodium acetate.
6. the method for claim 1, wherein said stablizer is organic boron nitrogenous compound.
7. method as claimed in claim 6, wherein said organic boron nitrogenous compound is borane-Trimethylamine 99 title complex.
8. method as claimed in claim 6, wherein said organic boron nitrogenous compound is borane-morpholine title complex.
9. method as claimed in claim 6, wherein said organic boron nitrogenous compound are octahydro three boric acid tetramethyl-ammoniums.
10. the method for claim 1, wherein said stablizer are borane-amine complex and the mixture of the about 1 weight % weak organic acid of about 0.005-.
11. the method for claim 1, wherein said stablizer are the alkali sulfite metal-salt.
12. the method for claim 1, wherein said stablizer are sulfurous acid.
13. a clarification, stable water or alcoholic solution, it comprises (a) is that the N-vinyl heterocyclic monomers that contains 3-6 ring carbon atom from the about 80 weight % of about 40-of the about 70 weight % of the about 10-of benchmark is the nitrogenous trivalent boron complexes of the about 2 weight % of the about 0.02-of benchmark in the multipolymer with the multipolymer of the vinyl comonomer of the about 20 weight % of about 60-and (b) in the composition total weight.
14. solution as claimed in claim 13, wherein the N-vinyl heterocyclic monomers for randomly on ring carbon atom by methyl substituted N-vinyl pyrrolidone or N-caprolactam.
15. solution as claimed in claim 14, wherein the N-vinyl heterocyclic monomers is the N-vinyl pyrrolidone.
16. solution as claimed in claim 13, wherein said comonomer is selected from lower acid vinyl ester, vinyl cyanide, vinylbenzene and composition thereof.
17. solution as claimed in claim 16, wherein said comonomer are vinyl-acetic ester, the monomeric weight ratio of monomer and copolymerization is the heterocyclic monomer of the about 80 weight % of about 50-: the vinyl-acetic ester of the about 20 weight % of about 50-.
18. solution as claimed in claim 17, wherein wt is than being the N-vinyl pyrrolidone of 55-70 weight %: the vinyl-acetic ester of 45-30 weight %.
19. solution as claimed in claim 13, wherein said boron coordinate compound is for being selected from borane-ammonia, the borane low-grade alkylamine, octahydro three boric acid four low alkyl group ammoniums, morpholine-borane, low alkyl group morpholine-borane, borane of the amino borane of silyl and composition thereof.
20. solution as claimed in claim 19, wherein said borane title complex is an organic compound.
21. solution as claimed in claim 20, wherein said borane title complex are octahydro three boric acid tetramethyl-ammoniums.
22. solution as claimed in claim 20, wherein said borane title complex is borane-TERTIARY BUTYL AMINE.
23. solution as claimed in claim 19, wherein said borane title complex is for containing the about 1 weight % organic acid borane-ammonia of about 0.005-.
24. solution as claimed in claim 23, wherein said organic acid are acetate.
25. solution as claimed in claim 13, the wherein about 0.2 weight % of about 0.05-of stabilizer comprises multipolymer.
26. the preparation of a use in personal care, it comprises the solution as claimed in claim 13 of effective film forming amount.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/355,137 US5534564A (en) | 1994-12-13 | 1994-12-13 | Process for the color stabilization of an aqueous N-vinyl heterocyclic copolymer solution |
| US08/355,137 | 1994-12-13 | ||
| US08/534,753 US5604275A (en) | 1994-12-13 | 1995-09-27 | Color stabilized aqueous n-vinyl heterocyclic copolymer solutions |
| US08/534,753 | 1995-09-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1217006A true CN1217006A (en) | 1999-05-19 |
Family
ID=26998714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95196697 Pending CN1217006A (en) | 1994-12-13 | 1995-11-29 | Color stabilization of aqueous heterocyclic copolymer |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0797618A4 (en) |
| CN (1) | CN1217006A (en) |
| WO (1) | WO1996018673A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3999022B2 (en) * | 2002-04-04 | 2007-10-31 | 株式会社日本触媒 | Vinyl pyrrolidone polymer |
| DE102005005974A1 (en) * | 2005-02-09 | 2006-08-10 | Basf Ag | Process for the stabilization of polyvinylpyrrolidones |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2634259A (en) * | 1951-07-31 | 1953-04-07 | Arnold Hoffman & Co Inc | Polymerization process for n-vinyl pyrrolidone |
| DE1270805B (en) * | 1955-12-27 | 1968-06-20 | Gen Aniline & Film Corp | Stabilization of polymeric N-vinyl-2-pyrrolidones |
| DE2540170C3 (en) * | 1975-09-10 | 1979-01-18 | Basf Ag, 6700 Ludwigshafen | Use of polyvinylpyrrolidone produced in organic solution for the production of stable aqueous polyvinylpyrrolidone-iodine solutions |
| US5319041A (en) * | 1993-03-26 | 1994-06-07 | Isp Investments Inc. | Process for the preparation of vinylpyrrolidone/vinyl acetate copolymers |
-
1995
- 1995-11-29 WO PCT/US1995/015434 patent/WO1996018673A1/en not_active Application Discontinuation
- 1995-11-29 EP EP95940854A patent/EP0797618A4/en not_active Withdrawn
- 1995-11-29 CN CN 95196697 patent/CN1217006A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| WO1996018673A1 (en) | 1996-06-20 |
| EP0797618A4 (en) | 1998-04-08 |
| EP0797618A1 (en) | 1997-10-01 |
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