CN101338003B - Method for preparing carboxylic acid-modified vinyl chloride-vinyl acetate copolymer resins - Google Patents
Method for preparing carboxylic acid-modified vinyl chloride-vinyl acetate copolymer resins Download PDFInfo
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- CN101338003B CN101338003B CN 200810041591 CN200810041591A CN101338003B CN 101338003 B CN101338003 B CN 101338003B CN 200810041591 CN200810041591 CN 200810041591 CN 200810041591 A CN200810041591 A CN 200810041591A CN 101338003 B CN101338003 B CN 101338003B
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Abstract
The invention provides a preparation method of vinyl chloride-vinyl acetate copolymer resin modified by carboxylic acid, which comprises the following steps: carrying out polymerization reaction of water, 60 to 90% the total amount of vinyl chloride, vinyl acetate, unsaturated single alkyl diacid ester or acrylic acid monomer, a dispersant, a link transfer agent, a pH buffer and an initiator at 50 to 70 DEG C and under the pressure of 0.5 to 1.2 MPa; starting to continuously add the balancing amount of vinyl chloride after the conversion rate of vinyl chloride is 15 to 20%; adding a reaction termination agent when the conversion rate of vinyl chloride is 75 to 85%; and collecting the target product from the reaction result. The method can successfully introduce carboxyl into a polymer link in a water phase environment through the structural transformation of unsaturated acid (anhydride) to eliminate the normal phenomena between a coating and a substrate such as stripping off, falling off and wrinkling, thereby improving each performance of the coating. The method uses no organic solvent and adopts a water phase suspension process to meet the requirements of clean production and environmental protection.
Description
Technical field
The present invention relates to adopt suspension polymerization to prepare the method for carboxyl acid modified vinyl chloride-vinyl acetate copolymer resins, unsaturated dibasic acid (acid anhydride) and C
2-C
6Alkyl unit alcohol esterification reaction, make the unsaturated acid mono alkyl ester, unsaturated acid mono alkyl ester or acrylic monomer and vinylchlorid (VC), vinyl acetate (VAc) make carboxylic vinyl chloride-vinyl acetate copolymer in the molecular chain in aqueous phase suspension polymerization.
Background technology
Vinyl chloride-vinyl acetate copolymer is based on vinylchlorid, carries out the polymkeric substance that copolymerization makes with vinyl acetate (or adding the 3rd monomer), general designation chlorine vinegar multipolymer.Characteristics such as technology is simple because it has, excellent property are widely used in floor tile, coating, printing ink, disc, tape and other purposes glue pastes etc.
Vinyl chloride-vinyl acetate resin has suspension method, emulsion method and solution method by the synthetic method branch, by the set of monomers composition, two yuan or terpolymer series product is arranged then.Adding the 3rd monomer or the 4th monomer raising vinyl chloride-vinyl acetate resin performance, making the resin functionalization is the approach commonly used of modification vinyl chloride-vinyl acetate resin, LG-DOW company adopts solution polymerization process to add a small amount of toxilic acid, vinyl alcohol or hydroxy acryl acid ester etc. in vinylchlorid and Vinyl Acetate Monomer polymerization system, make the vinyl chloride-vinyl acetate resin molecular structure functionization, in the copolymer molecule chain, introduce groups such as hydroxyl or carboxyl, can improve consistency, cohesive force between vinyl chloride-vinyl acetate resin and metal or plastic or other material.
Add unsaturated carboxylic acids (acid anhydride) such as fumaric acid, toxilic acid, methylene-succinic acid and vinylformic acid in the system and obtain carboxylic vinyl chloride-vinyl acetate resin, improved the cohesive force of vinyl chloride-vinyl acetate resin and metallic substrate surface, but dissolve each other owing to contain the general and water of carboxylic monomer, oiliness monomers such as vinylchlorid, vinyl acetate are difficult to and hydrophilic monomer when suspension polymerization, as generation copolyreaction such as unsaturated acid (acid anhydride).Therefore adopt the synthetic carboxy-modified vinyl chloride-vinyl acetate resin of solution polymerization process usually, as being dissolved in vinylchlorid, vinyl acetate and toxilic acid etc. in the butyl acetate solvent altogether, carry out polyreaction, US 4,476,035, US 4,323, and 628, US4,352,859 etc., can make carboxylic chlorine vinegar horse terpolymer resin in the molecular chain, but solution polymerization have after the polymerization solvent recuperation and remove, process such as rectifying, the cost height, technology is loaded down with trivial details, and solvent for use is unfriendly to environment, there is potential safety hazard, do not meet the requirement of current " green chemical industry " development.
Adopt the carboxy-modified vinyl chloride-vinyl acetate resin of suspension polymerization, compare with the solution polymerization process of common employing, simple, the cleaning of technology, production cost is low.But because the existence of WATER AS FLOW MEDIUM, unsaturated acid (acid anhydrides) etc. are soluble in water, and with vinylchlorid, vinyl acetate oil phase homophase not, difficulty fully contacts, and is difficult for taking place copolyreaction.
Summary of the invention
The objective of the invention is a kind of employing suspension polymerization and prepare carboxyl acid modified vinyl chloride-vinyl acetate copolymer resins, to overcome the above-mentioned defective that prior art exists.
Method of the present invention comprises the steps:
Vinylchlorid, vinyl acetate, unsaturated diacid mono alkyl ester or Acrylic Acid Monomer with water, gross weight 60-90%, dispersion agent, chain-transfer agent, pH buffer reagent and initiator, is under 0.5～1.2Mpa at 50 ℃-70 ℃ with pressure, carry out polyreaction, beginning adds the vinylchlorid of surplus continuously after the transformation efficiency of vinylchlorid is 15-20%, when the transformation efficiency of vinylchlorid is 75～85%, add reaction terminating agent, from reaction product, collect target product then;
The transformation efficiency of vinylchlorid is defined as follows:
The part by weight that adds the polymerization of vinyl choride monomer generation vinyl chloride-vinyl acetate copolymer in the still.
The weight consumption of water is 150～250% of a total monomer weight;
The weight consumption of dispersion agent is 0.1～1.5% of a total monomer weight;
The weight consumption of chain-transfer agent is 0.01～0.50% of a total monomer weight;
The weight consumption of pH buffer reagent is 0.01～0.1% of a total monomer weight;
The weight consumption of initiator is 0.01～0.1% of a total monomer weight;
Vinylchlorid, vinyl acetate, unsaturated diacid mono alkyl ester or acrylic monomer are monomer, and weight percent is:
Vinylchlorid 70-89%
Vinyl acetate 10-29%
Unsaturated diacid mono alkyl ester or acrylic monomer 0.1-3.0%
Described unsaturated diacid mono alkyl ester is the esterification reaction product of unsaturated diacid, unsaturated dicarboxylic anhydride or vinylformic acid and alcohol;
Described unsaturated diacid is selected from methylene-succinic acid, fumaric acid or toxilic acid;
Described unsaturated dicarboxylic anhydride is selected from itaconic anhydride, fumaric acid anhydride or maleic anhydride;
Described acrylic monomer is vinylformic acid or a-methacrylic acid;
Described alcohol is C
2-C
6Alkyl unit alcohol;
The preparation method of described unsaturated diacid mono alkyl ester is a prior art, as technology and the method for utilizing " organic chemistry " esterification to introduce, or adopts following method:
With unsaturated diacid or unsaturated dicarboxylic anhydride and C
2-C
6Alkyl unit alcohol is according to 1: 1.2～5 weight ratio, temperature 50-70 ℃ 0.5-2.0 of following reaction times hour, can obtain the unsaturated diacid mono alkyl ester of transformation efficiency about 50%;
Described dispersion agent is that alcoholysis degree is 70～85% polyvinyl alcohol, methylcellulose gum, ethyl cellulose, Vltra tears, polyacrylic acid or gelatin, preferably, described dispersion agent is the mixed dispersant of polyvinyl alcohol and Vltra tears, and preferred weight ratio is 1: 0.8～1.2;
Described PH buffer reagent is selected from sodium hydroxide, sodium bicarbonate or bicarbonate of ammonia etc., the present invention preferably uses bicarbonate of ammonia, it can improve the resin particle form, stop the generation of resin involucra, simultaneously guarantee that all the time system PH is in neutral range, avoid removing of HCl in the molecular chain, to improve the resin whiteness, resistance toheat is favourable;
Described chain-transfer agent major control molecular resin amount, promptly play the effect that reduces molecular weight, chain-transfer agent is selected from mercaptan compound, trieline, tetracol phenixin or 1-chloro-1-iodoethane etc., wherein to adopt mercaptan compound better, described mercaptan compound is selected from 2 mercapto ethanol, thioglycollic acid-2-ethyl hexyl ester, mercaptan such as isooctyl mercaptoacetate or ethylene glycol dimercapto acetate, be best with 2 mercapto ethanol again wherein, chain transfer can be once to add before polymerization, also can be that a part begins preceding adding in polymerization, another part begins certain hour in polymerization and adds, as adding gross weight 10～50% earlier, when polymerisation conversion reaches 15～30%, add the chain-transfer agent of surplus again;
Described reaction terminating agent stops the free radical activity effect for playing, and avoids side reaction, improves the resin whiteness, and reaction terminating agent is selected from acetone semicarbazone thiocarbamide, dihydroxyphenyl propane or Sodium Nitrite, and it adds weight is 0.010～0.030% of total monomer weight;
Described initiator mainly acts on and at high temperature produces free radical, trigger monomer generation polymeric chain increases, initiator be the special pentyl ester of the new enanthic acid tert-butyl ester of peroxidation, peroxidation trimethylacetic acid, peroxide tert pivalate ester or peroxy dicarbonate two-in (2-ethylhexyl) etc. more than one; Evaluation method: among the present invention following method is adopted in the evaluation of resin property:
The present invention is by unsaturated acid (acid anhydride) thaumatropy, carboxyl is successfully introduced in the macromolecular chain in aqueous environment, carboxyl when using in the vinyl chloride-vinyl acetate resin as coating can with substrate metal interionic generation chemical reaction, form chemical bond, improved the consistency and the cohesive force of resin and metallic substrate surface, thereby eliminated common peeling off between coating and base material, come off, phenomenon such as wrinkling has improved every performance of coating.The present invention does not with an organic solvent adopt aqueous-phase suspending technology, has reached to clean to produce and environmental requirement.
Embodiment
Embodiment 1
The first step: take by weighing 25g fumaric acid and 50g ethanol and add in the 250ml there-necked flask, rise heat to 65 ℃, stirring reaction 2.0hr obtains fumaric acid esterification reaction product, adds in the 10L polymermaking autoclave;
Second step: in the 10L polymeric kettle, add the 300g Vinyl Acetate Monomer simultaneously, 3500g water, 2.0g alcoholysis degree is 75% polyvinyl alcohol, 3.0g Vltra tears, weight concentration is 20% 0.20g mercaptoethanol, 0.50g bicarbonate of ammonia and 1200g vinyl chloride monomer, initiator peroxidation two-(3,5, the own ester of 5-trimethylammonium) the special butyl ester 0.40g of the new certain herbaceous plants with big flowers acid of 0.80g and peroxidation, be warming up to 65 ℃, pressure is to carry out polyreaction under the 0.88Mpa;
The 3rd step: polymerization 1.5hr, this moment, the transformation efficiency of vinylchlorid was 20%, the adding weight concentration is 0.15% the 0.50g mercaptoethanol aqueous solution, adds in 2 hours, adds the 500g vinyl chloride monomer simultaneously continuously, keep constant pressure, until adding monomer, the transformation efficiency that continues to react to vinylchlorid is 80% discharging, and slurry separates through whizzer, oven dry obtains product.
Embodiment 2
The first step is with embodiment 1; Second step added the 500g Vinyl Acetate Monomer simultaneously in the 10L polymeric kettle, the 1250g vinyl chloride monomer, and other technology is with embodiment 1, and pressure is 0.76Mpa; Polymerization 1.5hr in the 3rd step adds the 250g vinyl chloride monomer continuously, keeps constant pressure, and until adding monomer, other technology is with embodiment 1.
Embodiment 3
The first step: take by weighing 10g fumaric acid and 30g ethanol and add in the 100ml there-necked flask, rise heat to 65 ℃, stirring reaction 2.0hr obtains fumaric acid esterification reaction product, adds in the 10L polymermaking autoclave;
Second step and three step process are with embodiment 1.
Embodiment 4
The first step: take by weighing 50g fumaric acid and 120g ethanol and add in the 250ml there-necked flask, rise heat to 65 ℃, stirring reaction 2.0hr obtains fumaric acid esterification reaction product, adds in the 10L polymermaking autoclave;
Second step and three step process are with embodiment 1.
Embodiment 5
The first step: take by weighing 25g methylene-succinic acid and 50g butanols and add in the 250ml there-necked flask, rise heat, mix reaction 2.0hr, methylene-succinic acid esterification reaction product is added in the 10L polymermaking autoclave to 65 ℃.
Second step and three step process condition are with embodiment 1.
Embodiment 6
The first step: take by weighing 50g fumaric acid and 150g dehydrated alcohol and add in the 500ml there-necked flask, rise heat, mix reaction 2.0hr, fumaric acid esterification reaction product is added in the 10L polymermaking autoclave to 65 ℃.
Second step and three step process condition are with embodiment 1.
Embodiment 7
The first step: take by weighing 25g a-methacrylic acid, polymerization directly adds in the 10L polymermaking autoclave at the beginning.
Second step and three step process condition are with embodiment 1.
Embodiment 8
The first step: take by weighing 50g a-methacrylic acid, polymerization directly adds in the 10L polymermaking autoclave at the beginning.
Second step and three step process condition are with embodiment 1.
Embodiment 9
The first step: take by weighing 25g a-methacrylic acid.
Second step: polymerization begins to add continuously in the 10L polymermaking autoclave with volume pump, and other processing step is with embodiment 1.
Embodiment 10
The first step: take by weighing 25g fumaric acid and 50g dehydrated alcohol and add in the 250ml there-necked flask, rise heat, mix reaction 2.0hr, fumaric acid esterification reaction product is added in the 10L polymermaking autoclave to 70 ℃.
Second step: in the 10L polymeric kettle, add the 250g Vinyl Acetate Monomer simultaneously, the 3500g de-salted water, 2.5g alcoholysis degree is 75% polyvinyl alcohol, 2.0g Vltra tears, weight concentration is 20% 0.20g mercaptoethanol, 0.40g bicarbonate of ammonia, pressure testing vacuumizes, mix, add the 1250g vinyl chloride monomer, volume pump adds initiator peroxidation two-(3,5, the own ester of 5-trimethylammonium) 0.70g, the special butyl ester 0.50g of the new certain herbaceous plants with big flowers acid of peroxidation, chuck is warming up to 50 ℃, and pressure is 0.8Mpa insulation polymerization.
The 3rd step: polymerization 1.5hr, this moment, transformation efficiency was about 20%, and it is 0.15% the 0.50g mercaptoethanol aqueous solution that volume pump begins to add weight concentration, adds in 2 hours.Add simultaneously continuously the 500g vinyl chloride monomer, until adding monomer, continue to react to the transformation efficiency of vinylchlorid be 80%, discharging, slurry separates through whizzer, the test of oven dry post analysis.
Embodiment 11
The first step: take by weighing 40g vinylformic acid, polymerization directly adds in the 10L polymermaking autoclave at the beginning.
Second step and three step process condition are with embodiment 7.
Embodiment 12
The first step: take by weighing the acid of 25g maleic anhydride and add in the 250ml there-necked flask, rise heat, mix reaction 1.0hr, the maleic anhydride esterification reaction product is added in the 10L polymermaking autoclave to 60 ℃ with the anhydrous butanols of 50g.
Second step and three step process condition are with embodiment 7.
Comparative example 1
The first step: take by weighing the 25g toxilic acid and add in the 10L polymermaking autoclave.
Second step and three step process condition are with embodiment 1.
Comparative example 2
The first step: take by weighing the 50g toxilic acid and add in the 10L polymermaking autoclave.
Second step and three step process condition are with embodiment 1.
Comparative example 3
The first step: take by weighing the 50g methylene-succinic acid and add in the 10L polymermaking autoclave.
Second step and three step process condition are with embodiment 1.
Embodiment result gathers as table 1～3 time:
Table 1
Table 2
Table 3
Table 4
Claims (4)
1. the preparation method of carboxyl acid modified vinyl chloride-vinyl acetate copolymer resins, it is characterized in that, comprise the steps: water, the vinylchlorid of gross weight 60-90%, vinyl acetate and unsaturated diacid mono alkyl ester or Acrylic Acid Monomer, dispersion agent, chain-transfer agent, pH buffer reagent and initiator, is under 0.5～1.2Mpa at 50 ℃-70 ℃ with pressure, carry out polyreaction, beginning adds the vinylchlorid of surplus continuously after the transformation efficiency of vinylchlorid is 15-20%, when the transformation efficiency of vinylchlorid is 75～85%, add reaction terminating agent, from reaction product, collect target product then;
The weight consumption of water is 150～250% of a total monomer weight;
The weight consumption of dispersion agent is 0.1～1.5% of a total monomer weight;
The weight consumption of chain-transfer agent is 0.01～0.50% of a total monomer weight;
The weight consumption of pH buffer reagent is 0.01～0.1% of a total monomer weight;
The weight consumption of initiator is 0.01～0.1% of a total monomer weight;
Described monomer is vinylchlorid, vinyl acetate and unsaturated diacid mono alkyl ester or vinylformic acid, and weight percent is:
Vinylchlorid 70-89%
Vinyl acetate 10-29%
Unsaturated diacid mono alkyl ester or Acrylic Acid Monomer 0.1-3.0%.
2. method according to claim 1 is characterized in that: described unsaturated diacid mono alkyl ester is unsaturated diacid or unsaturated dicarboxylic anhydride and pure esterification reaction product.
3. method according to claim 2 is characterized in that, described unsaturated diacid is selected from methylene-succinic acid, fumaric acid or toxilic acid; Described unsaturated dicarboxylic anhydride is selected from itaconic anhydride, fumaric acid anhydride or maleic anhydride.
4. method according to claim 1 is characterized in that: described dispersion agent is that alcoholysis degree is 70～85% polyvinyl alcohol, methylcellulose gum, ethyl cellulose, Vltra tears, polyacrylic acid or gelatin;
Described PH buffer reagent is selected from sodium hydroxide, sodium bicarbonate or bicarbonate of ammonia;
Described chain-transfer agent is selected from mercaptan compound, trieline, tetracol phenixin or 1-chloro-1-iodoethane;
Described reaction terminating agent is selected from acetone semicarbazone thiocarbamide, dihydroxyphenyl propane or Sodium Nitrite;
Described initiator be the special pentyl ester of the new enanthic acid tert-butyl ester of peroxidation, peroxidation trimethylacetic acid, peroxide tert pivalate ester or peroxy dicarbonate two-in (2-ethylhexyl) more than one.
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