CN101665548B - PVC resin with ultra-low degree of polymerization and manufacturing method thereof - Google Patents
PVC resin with ultra-low degree of polymerization and manufacturing method thereof Download PDFInfo
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Abstract
The invention discloses a PVC resin with ultra-low degree of polymerization and a manufacturing method thereof. In the invention, a polymerization method is adopted to carry out polymerization reaction, the reaction temperature is 60-64 DEG C, and the reaction pressure is less than 1.0 MPa; a first chain transfer agent is added when the polymerization reaction is carried out for 0-30min, and then 0.005-0.012% of vinyl chloride monomer (VCM) is added; a second chain transfer agent is added when the polymerization reaction is carried out for 60-90min, and then 0.005-0.02% of monomer is added to obtain the PVC resin with ultra-low degree of polymerization. The PVC resin manufactured by the invention has the advantages of the average degree of polymerization below 500, high apparent density, low melting and gelatinization temperature, low melt viscosity, good transparency, short plasticization time and favorable processability and the like, and the phenomenon of accelerating products aging due to the transfer of plasticizer does not appear in machining process.
Description
Technical field
The present invention relates to a kind of polyvinyl chloride resin and working method thereof, relate in particular to a kind of PVC resin with ultra-low degree of polymerization and working method thereof.
Background technology
As everyone knows; During no chain-transfer agent, polymerization temperature is unique factor of decision SE molecular weight, and polymeric reaction temperature is high more; The molecular weight of PVC RESINS is low more; Therefore, obtain the very low PVC RESINS of mean polymerisation degree just needs very high temperature of reaction, even can reach more than 70 ℃.Raising along with temperature of reaction; Internal structure to polyvinyl chloride resin particle can produce very big influence: primary particle becomes big; The clinkering heighten degree has improved the solubleness of PVC RESINS in monomer etc., and formation closely reaches the granulated glass sphere particle easily, this must cause the reduction of resin particle interior porosity; The thermal decomposition rate of PVC RESINS constantly aggravates, and causes the thermostability of resin to reduce.Temperature of reaction is high more, and the corresponding raising of polymerization pressure can surpass 1.0MPa, the requirement that this is harsh more to the withstand voltage proposition of polymerization unit.Temperature of reaction is high more, also can cause sticking still serious, gives in the Production of PVC process and brings difficulty.Also have, along with the raising of temperature of reaction, polymerization also correspondingly requires to improve with the gelling temperature and the cloud point of dispersion agent, and this just causes polymerization to receive very big restriction with dispersion agent.
At present, produce the polyvinyl-chloride of low-polymerization degree resin and all adopt chain-transfer agent, to reduce temperature of reaction.Different chain-transfer agents is also inequality to the ability of SE molecular weight influence under identical concentration, and the polyvinyl chloride particles characteristic is also had very big influence, and this just needs to select suitable chain-transfer agent.
Adopting chain-transfer agent to produce the polyvinyl-chloride of low-polymerization degree resin also will consider under different transformation efficiencys; Chain transfer agent concentration is to the influence of SE molecular weight; This just needs to select suitable chain-transfer agent add-on, reinforced time and feed way, otherwise will make the PVC RESINS MWD wide, and the branchign of molecule degree is big; Cause the resin particle poor morphology, the problem of processing heat stability difference.
Summary of the invention
The objective of the invention is to overcome the problems referred to above of polyvinyl chloride resin of the prior art and working method existence thereof, a kind of PVC resin with ultra-low degree of polymerization and working method thereof are provided.The polyvinyl chloride resin mean polymerisation degree that the present invention produces reaches below 500; Have characteristics such as apparent density height, fusion and gelling temperature are low, melting viscosity is low, the transparency is good, fusion time is short, processing characteristics is good, in the course of processing, can not produce owing to goods aged phenomenon is quickened in plasticizer migration.
The technical scheme that the present invention adopts is following:
A kind of PVC resin with ultra-low degree of polymerization is characterized in that, comprises the component of following parts by weight:
100 parts of VCM vinyl chloride monomers,
150～200 parts of pure water,
0.4～0.7 part of dispersion agent,
0.02～0.04 part of buffer reagent,
0.04～0.09 part of initiator,
0.01～0.032 part of chain-transfer agent,
0.3～0.6 part of thermo-stabilizer,
0.3～0.6 part of terminator.
Said dispersion agent is a kind of among Z 150PH GH20, Z 150PH KH20 and the Z 150PH KH17 of Japanese synthetic chemistry company; And a kind of among the Vltra tears E50 of Dow Chemical company and the Vltra tears F50; A kind of compound with among the Z 150PH LL-02 of Japanese synthetic chemistry company and the Z 150PH LW-200, compositely proportional is 1: 1.2～2.0: 0.8～1.5.
Said initiator is a kind of compound in a kind of and peroxo-own ester of two-3,5,5 trimethylammoniums and the peroxo-dilaurate in peroxo-neodecanoic acid isopropyl benzene ester and the new peroxide tert-butyl caprate, and compositely proportional is 1: 1～2.
Said buffer reagent is bicarbonate of ammonia or sodium hydrogencarbonate.
Said chain-transfer agent is coloured glaze base ethanol, lauryl mercaptan or trieline.
Said thermo-stabilizer is organic zinc or organotin.
Said terminator is acetone semicarbazone thiocarbamide or αJia Jibenyixi.
A kind of working method of PVC resin with ultra-low degree of polymerization; It is characterized in that: adopt polymerization method to carry out polyreaction VCM vinyl chloride monomer, dispersion agent, initiator, pure water, buffer reagent, chain-transfer agent and thermo-stabilizer, 60～64 ℃ of temperature of reaction, reaction pressure is less than 1.0MPa;, polyreaction adds chain-transfer agent for the first time when beginning 0～30 minute; Add-on is 0.005～0.012% of a VCM vinyl chloride monomer amount, adds chain-transfer agent for the second time during in polyreaction to 60～90 minute, and add-on is 0.005～0.02% of an amount of monomer; As polymerization pressure decline 0.01～0.2MPa, add terminator and stop polyreaction.
Said dispersion agent is a kind of among Z 150PH GH20, Z 150PH KH20 and the Z 150PH KH17 of Japanese synthetic chemistry company; And a kind of among the Vltra tears E50 of Dow Chemical company and the Vltra tears F50; A kind of compound with among the Z 150PH LL-02 of Japanese synthetic chemistry company and the Z 150PH LW-200, compositely proportional is 1: 1.2～2.0: 0.8～1.5.
Said initiator is a kind of compound in a kind of and peroxo-own ester of two-3,5,5 trimethylammoniums and the peroxo-dilaurate in peroxo-neodecanoic acid isopropyl benzene ester and the new peroxide tert-butyl caprate.
Said buffer reagent is bicarbonate of ammonia or sodium hydrogencarbonate.
Said chain-transfer agent is coloured glaze base ethanol, lauryl mercaptan or trieline.
Said thermo-stabilizer is organic zinc or organotin.
Said terminator is acetone semicarbazone thiocarbamide or αJia Jibenyixi.
Employing the invention has the advantages that:
One, the present invention adopts ternary composite dispersing agent system; Adopt binary peroxide initiator system; Chain transfer is chosen in the specific reaction times according to specific ratio adding at twice, has improved the particle form and the MWD of resin; Improved the processing heat stability of resin, the polyvinyl chloride resin quality of being produced is better.
Two, the temperature of reaction in the polyreaction is 60～64 ℃; Reaction pressure is less than 1.0MPa; Under this temperature and pressure, carry out polyreaction and can reduce polymerization process to equipment and safe requirement, reaction process is more steady, also is more prone to control; Under this temperature, carry out the decomposition rate that polyreaction can reduce polyvinyl chloride resin, favourable to the thermostability that improves resin.
Three, among the present invention; Chain-transfer agent is pan feeding at twice; Select reinforced time of suitable chain-transfer agent and reinforced ratio, can reduce the effect of chain-transfer agent, can also reduce the influence of chain-transfer agent dispersant system to peroxide initiator; The polyvinyl chloride resin MWD of producing is more concentrated, and the ratio of low-molecular-weight resin is littler.
Four, the resin mean polymerisation degree that adopts the present invention to produce is stable, and control has characteristics such as apparent density height, fusion and gelling temperature are low, melting viscosity is low, the transparency is good, fusion time is short, processing characteristics is good easily.
Five, can not add softening agent in the course of processing, can not produce owing to goods aged phenomenon is quickened in plasticizer migration.
Six, this resin and other macromolecular materials have fabulous consistency and " intramolecularly plasticising " effect, and it is good to make goods transparency height, any surface finish, thermostability and flame retardant properties, are a kind of large usage quantities, PVC resin specially that purposes is wider.
Seven, the chain-transfer agent among the present invention is coloured glaze base ethanol, lauryl mercaptan or trieline, and under identical chain transfer agent concentration, what reduce polyvinyl chloride polymerization degree ability maximum is coloured glaze base ethanol; Next is a lauryl mercaptan, and the ability of trieline is minimum, and a large amount of coalescences of the thin basic ethanol fine drop of chain-transfer agent have not only promoted to pile up a large amount of formation of hole; The polyvinyl chloride resin particle that obtains is the many cells particle; The granule interior porosity increases, and in the collision of drop, merging process, the part dispersion agent of drop surface adsorption is also forced to take part feed liquor to drip inside; More dispersion agent can be adsorbed from aqueous phase again in drop surface after the merging; Disperse phase viscosity is reduced, and after coloured glaze base alcohol concn surpassed certain value, the IT of monomer-water also can improve; The deformation extent of drop reduces, and the polyvinyl chloride resin particulate regularity that therefore obtains is relatively good.
Eight, the chain-transfer agent among employing the present invention, as dredging basic ethanol, porosity reduces between the primary particle; Pile up porosity and obviously improve, increased the size of primary particle, weaken gathering; After having added coloured glaze base ethanol, the pore size distribution change is tending towards concentrated between particle, has improved the regularity of polyvinyl chloride resin.
Nine, the present invention adds the reinforced selection of time of chain-transfer agent when polyreaction begins 0～30 minute for the first time; Add during in polyreaction to 60～90 minute for the second time; So both guaranteed the add-on of chain-transfer agent; Under suitable transformation efficiency situation, add chain-transfer agent and can bring into play the regulating effect of chain-transfer agent to greatest extent the PVC RESINS molecular weight; Can reduce simultaneously the instantaneous concentration of chain-transfer agent in the polymerization system again to greatest extent, limit the influence of chain-transfer agent polymeric dispersant system and binary peroxide initiator system.
Ten, the polyvinyl chloride resin mean polymerisation degree of the present invention's production reaches below 500; Have characteristics such as apparent density height, fusion and gelling temperature are low, melting viscosity is low, the transparency is good, fusion time is short, processing characteristics is good, temperature of reaction, pressure are lower, and reaction process is controlled more easily; Requirement to polymerization unit is lower; The polyvinyl chloride resin particle of producing is more regular, and size distribution is more concentrated, and the resin mean polymerisation degree is stable.
Embodiment
Embodiment 1
A kind of PVC resin with ultra-low degree of polymerization comprises the component of following parts by weight:
100 parts of VCM vinyl chloride monomers,
150 parts of pure water,
0.4 part of dispersion agent,
0.02 part of buffer reagent,
0.04 part of initiator,
0.01 part of chain-transfer agent,
0.3 part of thermo-stabilizer,
0.3 part of terminator.
Wherein, Dispersion agent comprises Vltra tears E50 and the Z 150PH LL-02 of Japanese synthetic chemistry company of Z 150PH GH20, the Dow Chemical company of Japanese synthetic chemistry company, and Z 150PH GH20: Vltra tears E50: Z 150PH LL-02 is 1: 1.2: 0.8.
Initiator comprises peroxo-neodecanoic acid isopropyl benzene ester and the own ester of peroxo-two-3,5,5 trimethylammoniums, and peroxo-neodecanoic acid isopropyl benzene ester: peroxo-two-3, the own ester of 5,5 trimethylammoniums is 1: 1.
In addition, buffer reagent is selected bicarbonate of ammonia for use.Chain-transfer agent is selected coloured glaze base ethanol for use.Thermo-stabilizer is selected organic zinc for use.Terminator is selected the acetone semicarbazone thiocarbamide for use.
A kind of working method of PVC resin with ultra-low degree of polymerization adopts conventional polymerization method to carry out polyreaction VCM vinyl chloride monomer, dispersion agent, initiator, pure water, buffer reagent, chain-transfer agent and thermo-stabilizer, and temperature of reaction is controlled at 60 ℃; Reaction pressure is less than 1.0MPa; Before polyreaction begins, can add chain-transfer agent for the first time, add-on is 0.005% of a VCM vinyl chloride monomer amount, when polyreaction to 60 minute, adds chain-transfer agent for the second time; Add-on is 0.005% of an amount of monomer; As polymerization pressure decline 0.01MPa, promptly polymerisation conversion reaches at 75～85% o'clock, adds terminator and stops polyreaction.
Wherein, Dispersion agent is Z 150PH LL-02 compound of Vltra tears E50 and Japanese synthetic chemistry company of Z 150PH GH20, the Dow Chemical company of Japanese synthetic chemistry company; Compositely proportional is 1: 1.2: 0.8; Promptly Z 150PH GH20, Vltra tears E50 and Z 150PH LL-02 are dropped in the poly-unit, can mix the back and add, also can add respectively in this ratio.Different compositely proportionals can obtain the PVC RESINS of different performance index.Select composite dispersing agent can make the loose type resin of better performances, can make each item performance index of resin reach optimization.
Initiator is the compound of peroxo-neodecanoic acid isopropyl benzene ester and peroxo-two-3,5, the 5 own esters of trimethylammonium, and compositely proportional is 1: 1.According to the heat transfer efficiency of poly-unit with to the requirement of polymerization time; Carry out the compound requirement of satisfying polymerization process according to this ratio; Promptly peroxo-neodecanoic acid isopropyl benzene ester and the own ester of peroxo-two-3,5,5 trimethylammoniums are dropped in the poly-unit in this ratio; Can mix the back and add, also can add respectively.Use composite initiator not only can shorten polymerization time, and can improve the at the uniform velocity performance of polyreaction.
Above-mentioned compound being meant in proportion adds reaction material in the poly-unit, but the proportional mixing adding also can add respectively in proportion.
In addition, buffer reagent is selected bicarbonate of ammonia for use.Chain-transfer agent is selected coloured glaze base ethanol for use.Thermo-stabilizer is selected organic zinc for use.Terminator is selected the acetone semicarbazone thiocarbamide for use.
Embodiment 2
A kind of PVC resin with ultra-low degree of polymerization comprises the component of following parts by weight:
100 parts of VCM vinyl chloride monomers,
200 parts of pure water,
0.7 part of dispersion agent,
0.04 part of buffer reagent,
0.09 part of initiator,
0.032 part of chain-transfer agent,
0.6 part of thermo-stabilizer,
0.6 part of terminator.
Among the present invention; Dispersion agent comprises Vltra tears F50 and the Z 150PH LW-200 of Japanese synthetic chemistry company of Z 150PH KH20, the Dow Chemical company of Japanese synthetic chemistry company, and Z 150PH KH20: Vltra tears F50: Z 150PH LW-200 is 1: 2.0: 1.5.
Initiator comprises new peroxide tert-butyl caprate and peroxo-dilaurate, new peroxide tert-butyl caprate: the peroxo-dilaurate is 1: 2.
In addition, buffer reagent is a sodium hydrogencarbonate.Chain-transfer agent is a lauryl mercaptan.Thermo-stabilizer is an organotin.Terminator is a αJia Jibenyixi.
A kind of working method of PVC resin with ultra-low degree of polymerization adopts conventional polymerization method to carry out polyreaction, 64 ℃ of temperature of reaction VCM vinyl chloride monomer, dispersion agent, initiator, pure water, buffer reagent, chain-transfer agent and thermo-stabilizer; Reaction pressure is less than 1.0MPa; When polyreaction begins 30 minutes, add chain-transfer agent for the first time, add-on is 0.012% of a VCM vinyl chloride monomer amount, when polyreaction to 90 minute, adds chain-transfer agent for the second time; Add-on is 0.02% of an amount of monomer; As polymerization pressure decline 0.2MPa, promptly polymerisation conversion reaches at 75～85% o'clock, adds terminator and stops polyreaction.
Wherein, dispersion agent is Z 150PH LW-200 compound of Vltra tears F50 and Japanese synthetic chemistry company of Z 150PH KH20, the Dow Chemical company of Japanese synthetic chemistry company, and three's compositely proportional is 1: 2.0: 1.5.
Initiator comprises the compound of new peroxide tert-butyl caprate and peroxo-dilaurate, and the two compositely proportional is 1: 2.
In addition, buffer reagent is a sodium hydrogencarbonate.Chain-transfer agent is a lauryl mercaptan.Thermo-stabilizer is an organotin.Terminator is a αJia Jibenyixi.
Embodiment 3
A kind of PVC resin with ultra-low degree of polymerization comprises the component of following parts by weight:
100 parts of VCM vinyl chloride monomers,
170 parts of pure water,
0.55 part of dispersion agent,
0.03 part of buffer reagent,
0.07 part of initiator,
0.02 part of chain-transfer agent,
0.45 part of thermo-stabilizer,
0.5 part of terminator.
Among the present invention; Dispersion agent comprises Vltra tears E50 and the Z 150PH LW-200 of Japanese synthetic chemistry company of Z 150PH KH17, the Dow Chemical company of Japanese synthetic chemistry company, and Z 150PH KH17: Vltra tears E50: Z 150PH LW-200 is 1: 1.7: 1.1.
Initiator comprises peroxo-neodecanoic acid isopropyl benzene ester and peroxo-dilaurate, and oxidation neodecanoic acid isopropyl benzene ester: the peroxo-dilaurate is 1: 1.5.
In addition, buffer reagent is a bicarbonate of ammonia.Chain-transfer agent is a coloured glaze base ethanol.Thermo-stabilizer is an organotin.Terminator is a αJia Jibenyixi.
A kind of working method of PVC resin with ultra-low degree of polymerization is characterized in that: adopt conventional polymerization method to carry out polyreaction, 62 ℃ of temperature of reaction VCM vinyl chloride monomer, dispersion agent, initiator, pure water, buffer reagent, chain-transfer agent and thermo-stabilizer; Reaction pressure is less than 1.0MPa; When polyreaction begins 15 minutes, add chain-transfer agent for the first time, add-on is 0.008% of a VCM vinyl chloride monomer amount, when polyreaction to 75 minute, adds chain-transfer agent for the second time; Add-on is 0.0075% of an amount of monomer; When polymerization pressure decline 0.1MPa, promptly polymerisation conversion reaches at 75～85% o'clock, adds terminator and stops polyreaction.
Wherein, Dispersion agent is Z 150PH LW-200 compound of Vltra tears E50 and Japanese synthetic chemistry company of Z 150PH KH17, the Dow Chemical company of Japanese synthetic chemistry company, and Z 150PH KH17, Vltra tears E50 and Z 150PH LW-200 compositely proportional are 1: 1.7: 1.1.
Initiator is the compound of peroxo-neodecanoic acid isopropyl benzene ester and peroxo-dilaurate, and the compositely proportional of oxidation neodecanoic acid isopropyl benzene ester and peroxo-dilaurate is 1: 1.5.
In addition, buffer reagent is a bicarbonate of ammonia.Chain-transfer agent is a coloured glaze base ethanol.Thermo-stabilizer is an organotin.Terminator is a αJia Jibenyixi.
Embodiment 4
A kind of PVC resin with ultra-low degree of polymerization comprises the component of following parts by weight:
100 parts of VCM vinyl chloride monomers,
190 parts of pure water,
0.6 part of dispersion agent,
0.035 part of buffer reagent,
0.08 part of initiator,
0.030 part of chain-transfer agent,
0.5 part of thermo-stabilizer,
0.5 part of terminator.
Among the present invention; Dispersion agent comprises Vltra tears F50 and the Z 150PH LL-02 of Japanese synthetic chemistry company of Z 150PH KH20, the Dow Chemical company of Japanese synthetic chemistry company, and Z 150PH KH20: Vltra tears F50: Z 150PH LL-02 is 1: 1.9: 1.4.
Initiator comprises peroxo-neodecanoic acid isopropyl benzene ester and peroxo-dilaurate, and peroxo-neodecanoic acid isopropyl benzene ester: the peroxo-dilaurate is 1: 1.9.
A kind of working method of PVC resin with ultra-low degree of polymerization adopts conventional polymerization method to carry out polyreaction, 63.5 ℃ of temperature of reaction VCM vinyl chloride monomer, dispersion agent, initiator, pure water, buffer reagent, chain-transfer agent and thermo-stabilizer; Reaction pressure is less than 1.0MPa; When polyreaction begins 25 minutes, add chain-transfer agent for the first time, add-on is 0.011% of a VCM vinyl chloride monomer amount, when polyreaction to 85 minute, adds chain-transfer agent for the second time; Add-on is 0.01% of an amount of monomer; As polymerization pressure decline 0.18MPa, promptly polymerisation conversion reaches at 75～85% o'clock, adds terminator and stops polyreaction.
Wherein, Dispersion agent is Z 150PH LL-02 compound of Vltra tears F50 and Japanese synthetic chemistry company of Z 150PH KH20, the Dow Chemical company of Japanese synthetic chemistry company, and the compositely proportional of Z 150PH KH20, Vltra tears F50 and Z 150PH LL-02 is 1: 1.9: 1.4.
Initiator is the compound of peroxo-neodecanoic acid isopropyl benzene ester and peroxo-dilaurate, and the compositely proportional of peroxo-neodecanoic acid isopropyl benzene ester and peroxo-dilaurate is 1: 1.9.
Obviously; Those of ordinary skill in the art is according to technical know-how of being grasped and customary means; According to the above content, can also make the various ways that does not break away from basic fundamental thought of the present invention, these pro forma conversion are all within protection scope of the present invention.
Claims (6)
1. a PVC resin with ultra-low degree of polymerization is characterized in that, comprises the component of following parts by weight:
100 parts of VCM vinyl chloride monomers,
150～200 parts of pure water,
0.4～0.7 part of dispersion agent,
0.02～0.04 part of buffer reagent,
0.04～0.09 part of initiator,
0.01～0.032 part of chain-transfer agent,
0.3～0.6 part of thermo-stabilizer,
0.3～0.6 part of terminator;
Said dispersion agent is a kind of among Z 150PH GH20, Z 150PH KH20 and the Z 150PH KH17 of Japanese synthetic chemistry company; And a kind of among the Vltra tears E50 of Dow Chemical company and the Vltra tears F50; A kind of compound with among the Z 150PH LL-02 of Japanese synthetic chemistry company and the Z 150PH LW-200, compositely proportional is 1: 1.2～2.0: 0.8～1.5; Said initiator is a kind of compound in a kind of and peroxo-own ester of two-3,5,5 trimethylammoniums and the peroxo-dilaurate in peroxo-neodecanoic acid isopropyl benzene ester and the new peroxide tert-butyl caprate, and compositely proportional is 1: 1～2; Said polyvinyl chloride resin mean polymerisation degree≤500.
2. PVC resin with ultra-low degree of polymerization according to claim 1 is characterized in that: said buffer reagent is bicarbonate of ammonia or sodium hydrogencarbonate.
3. PVC resin with ultra-low degree of polymerization according to claim 1 and 2 is characterized in that: said chain-transfer agent is lauryl mercaptan or trieline.
4. PVC resin with ultra-low degree of polymerization according to claim 1 and 2 is characterized in that: said thermo-stabilizer is organic zinc or organotin.
5. PVC resin with ultra-low degree of polymerization according to claim 1 and 2 is characterized in that: said terminator is acetone semicarbazone thiocarbamide or alpha-methyl styrene.
6. the working method of a kind of PVC resin with ultra-low degree of polymerization according to claim 1; It is characterized in that: adopt polymerization method to carry out polyreaction VCM vinyl chloride monomer, dispersion agent, initiator, pure water, buffer reagent, chain-transfer agent and thermo-stabilizer; 60～64 ℃ of temperature of reaction; Reaction pressure adds chain-transfer agent for the first time less than 1.0MPa when polyreaction begins 0～30 minute, add-on is 0.005～0.012% of a VCM vinyl chloride monomer amount; Add chain-transfer agent for the second time during in polyreaction to 60～90 minute; Add-on is 0.005～0.02% of an amount of monomer, as polymerization pressure decline 0.01～0.2MPa, adds terminator and stops polyreaction.
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| CN104231307A (en) * | 2013-06-09 | 2014-12-24 | 上海氯碱化工股份有限公司 | Application of hydrotalcite-like compound, heat stabilizer, PVC resin with ultra-low polymerization degree and production method |
| CN107602745B (en) * | 2017-09-30 | 2019-12-24 | 北京化工大学 | Polyvinyl chloride nano particle with ultralow polymerization degree and preparation method thereof |
| CN109400784A (en) * | 2018-10-19 | 2019-03-01 | 新疆中泰化学股份有限公司 | Ultra low polymerization degree vinyl chloride-butyl acrylate copolymer resins and preparation method thereof |
| CN112745597B (en) * | 2020-12-28 | 2022-11-11 | 宜宾海丰和锐有限公司 | High-impact-resistance transparent PVC (polyvinyl chloride) medical material and preparation method thereof |
| CN113388055B (en) * | 2021-06-28 | 2023-01-31 | 天伟化工有限公司 | Low-polymerization-degree polyvinyl chloride special resin |
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