CN102702415A - Method for preparing chlorinated polyether resin - Google Patents
Method for preparing chlorinated polyether resin Download PDFInfo
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- CN102702415A CN102702415A CN2012101766485A CN201210176648A CN102702415A CN 102702415 A CN102702415 A CN 102702415A CN 2012101766485 A CN2012101766485 A CN 2012101766485A CN 201210176648 A CN201210176648 A CN 201210176648A CN 102702415 A CN102702415 A CN 102702415A
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Abstract
The invention discloses a method for preparing chlorinated polyether resin. The method comprises the following steps of: putting the following components in part by weight: 130 to 140 parts of first monomer chloroethylene, 35 to 50 parts of second monomer vinyl isobutyl ether, 1.0 to 2.5 parts of third monomer, 0.4 to 8 parts of dispersing agent, 0.3 to 0.6 part of initiator and 360 to 400 parts of deionized water into a reaction kettle, heating to the temperature of between 40 and 75 DEG C with stirring, performing polymerization reaction for 5 to 14 hours, stopping the reaction, dehydrating, drying and crushing to obtain the chlorinated polyether resin, wherein the third monomer may be one of vinyl versatate, vinyl neodecanoate, glycidyl versatate, vinyl acetate, ethyl acrylate, ethyl acrylate and butyl acrylate. The method is easy to operate and short in reaction time; the prepared chlorinated polyether resin is uniform in structure, high in ageing resistance, high in adhesive force and high in dissolvability and can be applied to the wide range.
Description
Technical field
The present invention relates to a kind of preparation method of resin, relate in particular to the preparation method of a kind of vinylchlorid and vinyl isobutyl ether copolymerization chlorinated polyether resin.
Background technology
Chlorinated polyether resin (MP) outward appearance is the pure white powder, and odorless is tasteless, nontoxic, is the random copolymers that vinylchlorid and VINYL ISOBUTYL ETHER adopt Raolical polymerizable to carry out copolymerization.The high molecular chain structure of chlorinated polyether resin polymkeric substance has determined itself distinctive performance.Isobutyl ether long chain alkyl group in the multipolymer exists as the side chain of macromolecular chain; Make the polymkeric substance polymer be difficult for piling up closely; Percent crystallinity reduces, and macro manifestations is that the snappiness of polymkeric substance strengthens, and explains that the vinyl isobutyl ether component has self-plasticizing action; Make filming of polymer formation not add the existing enough snappinesies of softening agent, thereby avoided making to film becoming fragile because adding the migration loss of external plasticizer.The existence of a large amount of ehter bonds makes polymer coating film and ground that good sticking power arranged, even at the aluminum and zinc metallic surface good sticking power is arranged also in the macromolecular chain.Do not contain saponifiable ester bond in the multipolymer, and very stable because of bonded chlorine atom, make coating have good water tolerance, chemicals-resistant corrodibility.Do not contain reactive pair of key in the chlorinated polyether resin, therefore be difficult for degrading for atmospheric oxidn, its coating resistance to weathering of processing is good, light fastness stability is excellent, be difficult for yellowing and efflorescence.So the coating of being processed by chlorinated polyether resin has good hydrolytic resistance, photostabilization, weathering resistance and chemical resistance.In addition, chlorinated polyether resin and other multiple macromolecular materials have good compatibility, event advantage capable of using own comes other resins are carried out modification.Like available its modified alkyd resin coating, can accelerate the trend of the rate of drying of phthalic resin coating, the weathering resistance that increases coating, minimizing disbonding.Because chlorinated polyether resin has above good performance, so obtaining good application aspect protective system, trade sales coating, frie retardant coating, food product containers and the package coating.
Chlorinated polyether resin generally adopts suspension polymerization and floating liquid polymer method at present; Because the limitation of vinylchlorid and the chemical property of vinyl isobutyl ether own; Cause the use properties of chlorinated polyether resin at aspects such as solvability, ageing resistances of being produced to satisfy the special user demand of some client, needed to add the above-mentioned performance that the 3rd monomer improves chlorinated polyether resin.
Like Chinese patent publication number 1401676A, open day is on March 12nd, 2003, denomination of invention: the preparation method of chlorinated polyether resin; This application case discloses a kind of preparation method of chlorinated polyether resin, and the moity of its prescription is following: vinylchlorid (VCM) 65～98%, vinyl isobutyl ether (VBM) the 2～35%, the 3rd monomer are unsaturated organic acids such as vinylformic acid, maleic anhydride; The 3rd monomeric weight is 0.03～5% of above-mentioned total monomer weight, polymerization in water, and the weight of water is 1～5 times of above-mentioned total monomer weight; Drop into dispersion agent, emulsifying agent, initiator etc.; Polymerization temperature: 40～80 ℃, constantly stir polymerization reaction time during polymerization; 3～10 hours.Its weak point is that this method is typical suspension polymerization process, and product is dissolved with residue, lysate is muddy, and the product resistance to deterioration is poor.
And for example Chinese patent publication number CN101580569A discloses day on November 18th, 2009, and denomination of invention: chemically modified chlorinated polyether resin and anticorrosive coating thereof, this application case relates to a kind of chemically modified chlorinated polyether resin and anticorrosive coating thereof.It is carbon-carbon double bonds monomer and chlorinated polyether resin through chemical reaction and the chlorinated polyether resin of modification, its viscosity is 1000～2500MPa.s; The reactant consumption of said chemical reaction is: 1 weight part chlorinated polyether resin, 2～4 weight part carbon-carbon double bonds monomers, 3～5 weight part YLENE and 0.03～0.05 weight part mixed initiator; Wherein the carbon-carbon double bonds monomer is one or more in ethyl propenoate, Bing Xisuandingzhi, 2-EHA, TEB 3K, NSC 20956, the vinylbenzene; Mixed initiator is that weight ratio is the Lucidol of 0.5～3:1 and the mixture of Diisopropyl azodicarboxylate.Weak point is that the product viscosity of this method production is big, can only be applied to the protective system industry, and range of application receives very big restriction; This method is to improve with the finished product chlorinated polyether resin in addition, and technology is loaded down with trivial details.
Summary of the invention
The present invention has overcome the defective of prior art, and a kind of simple to operate, the product resistance to deterioration is good, solubility property the is good vinylchlorid and the preparation method of vinyl isobutyl ether copolymerization chlorinated polyether resin are provided.
In order to solve the problems of the technologies described above; The present invention realizes through following technical scheme: a kind of preparation method of chlorinated polyether resin; By weight with 130 ~ 140 parts in the first monomer vinylchlorid, 35 ~ 50 parts of the second monomer vinyl isobutyl ethers, 1.0 ~ 2.5 parts of the 3rd monomers; 0.4 ~ 8 part of dispersion agent; 0.3 ~ 0.6 part of initiator in 360 ~ 400 parts of input reaction kettles of deionized water, under agitation is warming up to 40 ~ 75 ℃ of polyreactions termination reaction after 5 ~ 14 hours; Dehydration, dry, pulverize and promptly get chlorinated polyether resin, said the 3rd monomer is a kind of in tertiary ethylene carbonate, neodecanoic acid vinyl ester, tertiary carbonic acid glycidyl ester, vinyl acetate, ethyl propenoate, the Bing Xisuandingzhi.
Further:
Among the present invention 30～65% of the first monomer vinylchlorid weight, add with the mode of adding continuously in reaction beginning back, adding speed is 120～300g/h.
Dispersion agent of the present invention is two or more the mixture in methylcellulose gum, sodium lauryl sulphate, TX10 (TX-10), α-allyl group TX10 [10] ammonium sulfate (HS-10), the hydroxypropylcellulose.
Initiator of the present invention be the peroxo-trimethylacetic acid tert-butyl ester (TX-25), new peroxide tert-butyl caprate (TX-23), peroxy dicarbonate two (2-ethylhexyl) (EHP), the mixture of one or more in the peroxo-neodecanoic acid isopropyl benzene ester (TX-99).
Temperature of reaction of the present invention is 50～60 ℃.
Reaction times of the present invention is 8～12 hours.
The present invention is on the basis of traditional chlorinated polyether resin preparation; Improved the 3rd monomeric kind; Use tertiary ethylene carbonate, neodecanoic acid vinyl ester, tertiary carbonic acid glycidyl ester, vinyl acetate, ethyl propenoate, Bing Xisuandingzhi ester class etc. as the 3rd monomer; Because the big hydrophobic branched structure of the 3rd monomer ubiquity that adds, the ageing resistance that this just provides chlorinated polyether resin has increased solvent compatibility; Reduced the viscosity of resin, chlorinated polyether resin can be used in wider scope.
The 3rd monomeric amount that adds is very big to the performance impact of chlorinated polyether resin, and the 3rd monomeric add-on can not play the effect that changes resin property very little; The 3rd monomeric add-on is too big, increases production cost, and the 3rd monomeric add-on increases to a certain degree, and product performance are improved not obviously when continuing to add people's the 3rd monomer, consider economy, and the 3rd amount of monomer of adding can not be too many.Therefore the parts by weight that the 3rd monomer adds among the present invention are 1.0 ~ 2.5 parts.
Because vinylchlorid and vinyl isobutyl ether reactivity ratio in polymerization process differ greatly (reactivity ratio of vinylchlorid is 100 times of vinyl isobutyl ether); Therefore this has just caused the chlorinated polyether resin molecule segment that the polymerization process different times is produced on microcosmic to form different; Relative molecular weight distributes wide, thereby has caused macroscopical performance decrease such as chlorinated polyether resin solvability, sticking power that go up.The present invention is employed in the method for adding vinylchlorid in the polymerization process and adds vinylchlorid; Make the chlorinated polyether resin molecular structure basically identical that is generated at the polymerization process different times; Make resin structure homogeneous more, further improved performances such as chlorinated polyether resin solvability, sticking power.
Advantage of the present invention is: the present invention is simple to operate; Reaction times is short, owing to improved the 3rd monomeric kind, the chlorinated polyether resin structure of preparation is homogeneous more; Improved the performance such as anti-aging, solvability of chlorinated polyether resin, chlorinated polyether resin can be used in wider scope.Chlorinated polyether resin of the present invention can be dissolved in aromatic hydrocarbon such as toluene, YLENE, also can be dissolved in ester class, ketone equal solvent, good, the no residue of the solution transparency of processing; Toluene solution 20%, the viscosity in the time of 23 ℃ can satisfy the requirement that coating and printing ink are used between 20 ~ 70mPa.S; The dry resin powder was deposited 24 hours under 80 ℃ of conditions, and the color of resin no change still is a white.
Embodiment
Below through embodiment the present invention is done and to describe in further detail, but the present invention is not limited to described embodiment.
Embodiment 1:
With the first monomer vinylchlorid 850g; The second monomer vinyl isobutyl ether 350g, deionized water 3600g, methylcellulose gum 1g, sodium lauryl sulphate 2g, TX10 2g; The 3rd monomer tertiary ethylene carbonate 17g; New peroxide tert-butyl caprate (TX-23) 5g drops into polymeric kettle, stirs and is warming up to 50 ℃, the beginning polyreaction; Reaction beginning back adds vinylchlorid 500g altogether with the speed of 150g/h, react termination reaction after 14 hours, dehydration, drying, pulverize the resin of viscosity 65mPa.S.Viscosity measurement: resin concentration is 20% toluene solution, and the viscosity in the time of 23 ℃ records with NDJ-1 type viscometer; Transparent, the no residue of 30% xylene solution (3g chlorinated polyether resin, 7g YLENE stir and processed solution in 20 minutes, estimate its transparency); The dry resin powder was deposited 24 hours under 80 ℃ of conditions, and the color of resin no change still is a white.
Embodiment 2:
With the first monomer vinylchlorid 800g; The second monomer vinyl isobutyl ether 400g; Deionized water 4000g; Sodium lauryl sulphate 2g, TX10 3g, α-allyl group TX10 [10] ammonium sulfate 2g, the 3rd monomer tertiary carbonic acid glycidyl ester 16g, peroxy dicarbonate two (2-ethylhexyl) (EHP) 5g drop into polymeric kettle; Stirring is warming up to 53 ℃, the beginning polyreaction; Reaction beginning back adds vinylchlorid 550g altogether with the speed of 300g/h, react termination reaction after 12 hours, dehydration, drying, pulverize the resin of viscosity 45mPa.S.Viscosity measurement: resin concentration is 20% toluene solution, and the viscosity in the time of 23 ℃ records with NDJ-1 type viscometer; Transparent, the no residue of 30% xylene solution (3g chlorinated polyether resin, 7g YLENE stir and processed solution in 20 minutes, estimate its transparency); The dry resin powder was deposited 24 hours under 80 ℃ of conditions, and the color of resin no change still is a white.
Embodiment 3:
With the first monomer vinylchlorid 800g; The second monomer vinyl isobutyl ether 400g; Deionized water 4000g, methylcellulose gum 2g, α-allyl group TX10 [10] ammonium sulfate 4g, hydroxypropylcellulose 2g; The 3rd monomer vinyl acetate 20g, the peroxo-trimethylacetic acid tert-butyl ester (TX-25) 6g drops into polymeric kettle; Stirring is warming up to 57 ℃, the beginning polyreaction; Reaction beginning back adds vinylchlorid 600g altogether with the speed of 120g/h, react termination reaction after 8 hours, dehydration, drying, pulverize the resin of viscosity 35mPa.S.Viscosity measurement: resin concentration is 20% toluene solution, and the viscosity in the time of 23 ℃ records with NDJ-1 type viscometer; Transparent, the no residue of 30% xylene solution (3g chlorinated polyether resin, 7g YLENE stir and processed solution in 20 minutes, estimate its transparency); The dry resin powder was deposited 24 hours under 80 ℃ of conditions, and the color of resin no change still is a white.
Embodiment 4:
With the first monomer vinylchlorid 700g; The second monomer vinyl isobutyl ether 500g; Deionized water 4000g, TX10 1g, α-allyl group TX10 [10] ammonium sulfate 2g, hydroxypropylcellulose dispersion agent 1g, the 3rd monomer butyl acrylate 19g; The peroxo-trimethylacetic acid tert-butyl ester (TX-25) 4g, peroxo-neodecanoic acid isopropyl benzene ester (TX-99) 1g drops into polymeric kettle; Stirring is warming up to 60 ℃, the beginning polyreaction; Reaction beginning back adds vinylchlorid 700g altogether with the speed of 200g/h, react termination reaction after 5 hours, dehydration, drying, pulverize the resin of viscosity 25mPa.S.Viscosity measurement: resin concentration is 20% toluene solution, and the viscosity in the time of 23 ℃ records with NDJ-1 type viscometer; Transparent, the no residue of 30% xylene solution (3g chlorinated polyether resin, 7g YLENE stir and processed solution in 20 minutes, estimate its transparency); The dry resin powder was deposited 24 hours under 80 ℃ of conditions, and the color of resin no change still is a white.
Embodiment 5:
With the first monomer vinylchlorid 500g; The second monomer vinyl isobutyl ether 500g, deionized water 4000g, TX10 2g, hydroxypropylcellulose dispersion agent 3g; The 3rd monomer tertiary carbonic acid glycidyl ester 17g, peroxo-neodecanoic acid isopropyl benzene ester (TX-99) 3g drops into polymeric kettle; Stirring is warming up to 65 ℃, the beginning polyreaction; Reaction beginning back adds vinylchlorid 800g altogether with the speed of 180g/h, react termination reaction after 5 hours, dehydration, drying, pulverize the resin of viscosity 25mPa.S.Viscosity measurement: resin concentration is 20% toluene solution, and the viscosity in the time of 23 ℃ records with NDJ-1 type viscometer; Transparent, the no residue of 30% xylene solution (3g chlorinated polyether resin, 7g YLENE stir and processed solution in 20 minutes, estimate its transparency); The dry resin powder was deposited 24 hours under 80 ℃ of conditions, and the color of resin no change still is a white.
Comparative Examples:
With the first monomer vinylchlorid 800g; The second monomer vinyl isobutyl ether 400g; Deionized water 4000g; Sodium lauryl sulphate 2g, TX10 3g, α-allyl group TX10 [10] ammonium sulfate 2g, peroxy dicarbonate two (2-ethylhexyl) (EHP) 5g drop into polymeric kettle; Stirring is warming up to 53 ℃, the beginning polyreaction; Reaction beginning back adds vinylchlorid 550g altogether with the speed of 300g/h, reacts termination reaction after 12 hours; Dehydration, dry, pulverize the resin of viscosity 45mPa.S.Viscosity measurement: resin concentration is 20% toluene solution, and the viscosity in the time of 23 ℃ records with NDJ-1 type viscometer; 30% xylene solution (3g chlorinated polyether resin, 7g YLENE stir and processed solution in 20 minutes, estimate its transparency) omits muddiness, residue is arranged; The dry resin powder was deposited 24 hours under 80 ℃ of conditions, and resin becomes yellow by original white powder.
Can find out through above Comparative Examples, chlorinated polyether resin has been introduced the 3rd monomer in polymerization process after, change the molecular structure of resin, ageing-resistant performance, the solubility property of resin had obvious improvement.
Claims (6)
1. the preparation method of a chlorinated polyether resin, by weight with 130 ~ 140 parts in the first monomer vinylchlorid, 35 ~ 50 parts of the second monomer vinyl isobutyl ethers; 1.0 ~ 2.5 parts of the 3rd monomers; 0.4 ~ 8 part of dispersion agent, 0.3 ~ 0.6 part of initiator is in 360 ~ 400 parts of input reaction kettles of deionized water; Under agitation be warming up to 40 ~ 75 ℃ of beginning polyreactions; React termination reaction after 5 ~ 14 hours, dehydration, dry, pulverize and promptly get chlorinated polyether resin, it is characterized in that said the 3rd monomer is a kind of in tertiary ethylene carbonate, neodecanoic acid vinyl ester, tertiary carbonic acid glycidyl ester, vinyl acetate, ethyl propenoate and the Bing Xisuandingzhi.
2. the preparation method of chlorinated polyether resin according to claim 1 is characterized in that 30～65% of the said first monomer vinylchlorid weight, adds with the mode of adding continuously in reaction beginning back, and adding speed is 120～300g/h.
3. the preparation method of chlorinated polyether resin according to claim 1 is characterized in that described dispersion agent is two or more the mixture in methylcellulose gum, sodium lauryl sulphate, TX10, α-allyl group TX10 [10] ammonium sulfate, the hydroxypropylcellulose.
4. the preparation method of chlorinated polyether resin according to claim 1; It is characterized in that described initiator is the peroxo-trimethylacetic acid tert-butyl ester, new peroxide tert-butyl caprate, peroxy dicarbonate two (2-ethylhexyl), the mixture of one or more in the peroxo-neodecanoic acid isopropyl benzene ester.
5. the preparation method of chlorinated polyether resin according to claim 1 is characterized in that described temperature of reaction is 50～60 ℃.
6. the preparation method of chlorinated polyether resin according to claim 1 is characterized in that the described reaction times is 8～12 hours.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107602751A (en) * | 2017-09-08 | 2018-01-19 | 北京化工大学 | A kind of low molecule amount hydroxyl chlorinated polyether resin and preparation method thereof |
| CN111234085A (en) * | 2020-03-17 | 2020-06-05 | 杭州电化集团有限公司 | Formula and preparation method of bulk polymerization chlorinated polyether resin |
| CN111876032A (en) * | 2020-08-05 | 2020-11-03 | 广西镀宝环保科技有限公司 | Water-based rust conversion industrial coating and preparation method thereof |
| CN112625164A (en) * | 2020-12-18 | 2021-04-09 | 杭州电化新材料有限公司 | Functional group monomer modified water-based epichlorohydrin emulsion and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1401676A (en) * | 2002-09-28 | 2003-03-12 | 刘琳 | Process for preparing chloro-ether resin |
| CN101580569A (en) * | 2009-06-22 | 2009-11-18 | 中国海洋石油总公司 | Chemically modified chlorinated polyether resin and anticorrosive coating thereof |
-
2012
- 2012-05-29 CN CN2012101766485A patent/CN102702415A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1401676A (en) * | 2002-09-28 | 2003-03-12 | 刘琳 | Process for preparing chloro-ether resin |
| CN101580569A (en) * | 2009-06-22 | 2009-11-18 | 中国海洋石油总公司 | Chemically modified chlorinated polyether resin and anticorrosive coating thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107602751A (en) * | 2017-09-08 | 2018-01-19 | 北京化工大学 | A kind of low molecule amount hydroxyl chlorinated polyether resin and preparation method thereof |
| CN111234085A (en) * | 2020-03-17 | 2020-06-05 | 杭州电化集团有限公司 | Formula and preparation method of bulk polymerization chlorinated polyether resin |
| CN111234085B (en) * | 2020-03-17 | 2022-04-12 | 杭州电化集团有限公司 | Formula and preparation method of bulk polymerization chlorinated polyether resin |
| CN111876032A (en) * | 2020-08-05 | 2020-11-03 | 广西镀宝环保科技有限公司 | Water-based rust conversion industrial coating and preparation method thereof |
| CN112625164A (en) * | 2020-12-18 | 2021-04-09 | 杭州电化新材料有限公司 | Functional group monomer modified water-based epichlorohydrin emulsion and preparation method thereof |
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Application publication date: 20121003 |