CN102453176A - Preparation method of PVC (polrvinyl chloride) resin with high porosity and low film coverage rate - Google Patents
Preparation method of PVC (polrvinyl chloride) resin with high porosity and low film coverage rate Download PDFInfo
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- CN102453176A CN102453176A CN2010105151781A CN201010515178A CN102453176A CN 102453176 A CN102453176 A CN 102453176A CN 2010105151781 A CN2010105151781 A CN 2010105151781A CN 201010515178 A CN201010515178 A CN 201010515178A CN 102453176 A CN102453176 A CN 102453176A
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Abstract
The invention discloses a preparation method of a PVC resin with high porosity and low film coverage rate, which adopts suspension polymerization. The preparation method is characterized in that the preparation method comprises the following steps: 1, adding water, a vinyl chloride monomer, a composite dispersion system, a porosity conditioning agent, a chain transferring agent, a pH buffer and an initiator to a polymerization reactor; 2, carrying out a polymerization reaction on above materials in the polymerization reactor under conditions that the pressure is 0.90-1.20MPa and the temperature is 50-75DEG C; 3, adding a reaction terminator when the polymerization temperature is maintained and the polymerization pressure is decreased to 0.1-0.30MPa; 4, discharging the residual vinyl chloride monomer; and 5, collecting the target product from reaction products, wherein the composite dispersion system is a mixture of partially-alcoholized polyvinyl alcohol and partially-alcoholized hydroxypropyl methyl cellulose. The PVC resin prepared with the method disclosed in the invention has the advantages of high porosity, less fisheye, low film coverage rate, structured particle form, concentrated resin particle size distribution, and easy residual monomer removal.
Description
Technical field
This present invention belongs to the high molecular polymerization field, particularly the preparation method of low polymerization degree, high porosity and low epithelium fraction of coverage PVC RESINS.
Background technology
Polyvinyl-chloride of low-polymerization degree (PVC) resin is meant that generally the polymerization degree is at the SE below 800 (PVC) resin.Because its molecular weight is low, apparent density is high, melt fluidity good; Fusion time is short; Be easy to characteristics such as processing, all be widely used at manufacturing sheet material, injection moulding pipe fitting, blow molding and modified resin aspects such as (chlorinated polyvinyl chloride resin are produced in chlorination like the degree of depth).
But the PVC resin with low degree of polymerization porosity is low, and resin particle is tightr, and the particle epithelium that dispersion agent and vinylchlorid graft copolymerization produce is thicker, influences the processing characteristics and the further modification of resin.
PVC resin with low degree of polymerization is carried out chlorination modified processing, and the chlorinated polyvinyl chloride that makes (CPVC) resin has good resistance toheat, generally can be under 95 ℃ high temperature life-time service, be higher than about 35 ℃ in PVC goods.The CPVC resin has obtained widespread use as a kind of heat-resistant engineering plastic of excellent property at home and abroad at aspects such as extruding heat-resisting pipes, sheet material or injection heat pipe connecting piece.Produce in the process of CPVC resin at chlorination PVC,, remove and improve chloridization process in order to improve the processing flowability and the product properties of gained CPVC resin; Improve outside the chlorination technique level, it also is vital selecting suitable chlorating PVC resin with low degree of polymerization for use, helps chlorination in order to make polyvinyl chloride resin; Requirement polyvinyl chloride resin is loose; Internal void is many and even, epithelium the least possible (discontinuous, local exposed), and the particle regularity is good.The CPVC PVC resin specially has following characteristics on structure and performance: (1) resin polymerization degree is lower.(2) the resin apparent density is lower, short texture, and porosity is high.(3) epithelium of resin particle is thin as much as possible, even lacks skin or do not have skin.
The method of making the resin loose porous, that the epithelium fraction of coverage is low is equipped with the variation of power of agitator mainly around the adjustment to polymer dispersion system, control PVC granulating process.
U.S. B.F.Goodrich chemical company has released the many pieces of patented technologies of making no skin or few skin porous PVC resin, like US4, and 711; 908, US4,775,701, US4; 775,702, US4,742; 085 etc., this technology is used in the suspension polymerization of VC system, and the special dispersion system that is adopted is mainly formed as follows: (a) a kind of unneutralized ion-sensitive dispersion agent of water medium thickening that can make is made main dispersant; (b) Z 150PH of certain alcoholysis degree; When VCM transformation efficiency during at 1-5%; A kind of ionic compound that adds q.s; This ionic compound gets off the ion-sensitive main dispersant that accounts for main amount in the dispersion system from VCM droplet surface desorption, to produce the polyvinyl chloride resin of no skin or few skin, high porosity.This technology adopts the dispersion agent kind more special, complicated operation, and difficult control granulating process is prone to situation such as coarse fodder, seize.
Simultaneously; B.F.Goodrich chemical company is also at patent US4; Released in 963,592 and a kind ofly can regulate the New-type adjuvant that the molecular resin amount can improve the resin voids rate again, like 2-sulfydryl phenylpropyl alcohol thiazole, 2-sulfydryl phenylpropyl alcohol oxazole, 2-sulfydryl benzimidazole etc.; But this auxiliary agent makes the resin particle chap easily, exceeds normal range.
Japan is special disclose 57,14607, adopts the mode that in batches adds dispersion agent to reduce the polyvinyl chloride resin epithelium, and adding cellulose family dispersion agent is produced to such an extent that the resin fusion is easy between the 5-40% transformation efficiency, very good to plasticizer absorption, flake is few.But adopt this kind method resin particle size to be not easy control, go out coarse fodder easily, and the industriallization operability is not strong.
The Shanghai chlor-alkali is delivered patent and is produced high porosity resin; CN1927898A, the compound dispersing agent that a kind of low alcoholysis level, low viscous PVA and HPMC form, a kind of porosity regulator is an auxiliary agent; Carry out suspension polymerization of VC; Produce high porosity resin, but resin surface epithelium exposed part is less, the less and skewness of internal void.
The Shanghai chlor-alkali is delivered a kind of method that reduces the PVC RESINS of epithelium raising porosity of patent; CN101717459A; Comprise the steps: to add a kind of high alcoholysis degree Z 150PH, a kind of middle alcoholysis degree Z 150PH and other auxiliary agent and vinyl chloride monomer before (1) polymerization, begin polymerization with certain power of agitator; (2) during polymerisation conversion 12-20%, add a kind of polyvinyl alcohol with low alcoholysis level, improve power of agitator; (3) during polymerisation conversion 30-45%, add a certain amount of polyvinyl alcohol with low alcoholysis level once more, change power of agitator to finishing polymerization.The resin particle diameter that uses present method to produce is generally bigger, is prone to coarse fodder, and complicated operation.
The patent CN87 of domestic Zhejiang University, 1,01663A is main dispersant with the Marinco H; With two types of porosity regulators of different nature is auxilliary dispersion agent, is auxiliary agent with the water-soluble inorganic salt, carries out suspension polymerization of VC; Preparation is loose, graft-less copolymer forms epithelium and the high polyvinyl chloride particles of apparent density; And the method for minimizing kettle pasting matter, but resin particle is very thick, and technology still can't be used.
Summary of the invention
The technical issues that need to address of the present invention provide the preparation method of the PVC RESINS of a kind of low polymerization degree and high porosity, low epithelium fraction of coverage; The PVC RESINS sedimentation that makes is high, flake is few; The epithelium fraction of coverage is low; Particle form is regular, and the resin centralized particle diameter is prone to remove residual monomer.
The preparation method of the PVC RESINS of the low epithelium fraction of coverage of a kind of high porosity of the present invention; Be that water, vinyl chloride monomer, composite dispersing agent, porosity regulator, chain-transfer agent, PH buffer reagent and initiator are added in the polymeric kettle; Under the pressure of 0.90-1.20MPa, be provided with in the polymerization reaction kettle of whipping appts, carry out polyreaction under 50 ℃-75 ℃; When keeping polymerization temperature to polymerization pressure decline 0.1-0.30MPa; Add reaction terminating agent, discharge remaining VCM monomer, from reaction product, collect title product then.
Said compound dispersing agent is the Z 150PH of two kinds of partial alcoholysis and the mixture of Vltra tears (HPMC);
The Z 150PH of said two kinds of partial alcoholysis comprises Z 150PH (I) and a kind of low alcoholysis level, the full-bodied Z 150PH (II) of a kind of high alcoholysis degree, medium viscosity;
The alcoholysis degree of the PVAC polyvinylalcohol (I) of said high alcoholysis degree, medium viscosity is 70-90% (x), 78-82% preferably, and viscosity is 40-55mPa.s (under 20 ℃, measuring during 4% concentration) preferably.This dispersion agent can make the surface tension of system reduce, and plays the guarantor's glue ability of coordination system and the effect of dispersive ability, makes polymerization system when keeping certain protection drop ability, takes into account dispersive ability, prevents sticking still, hangs oar.
The alcoholysis degree of said low alcoholysis level, full-bodied PVAC polyvinylalcohol (II) is 40-50% (x), 42-46% preferably, and viscosity is 60-120mPa.s (under 25 ℃, measuring during 35% concentration) preferably.This dispersion agent is oil soluble; In the chloroethylene polymerization process, can exert an influence to primary particle in the polyvinyl chloride particles and aggregate thereof; Improve the porousness of resin particle, improve resin internal void homogeneity, reduce resin particle surface epithelium accordion condition.
The methoxy content of said HPMC is 20-40%, preferably 25-35%; Hydroxypropyl content 5-15%, preferably 5-10%.Viscosity is 30-70mPa.s (20 ℃ are measured during 2% concentration), preferably 40-60mPa.s; HPMC plays in system and disperses the effect of VCM drop, simultaneously the VCM drop is had certain protective role, is attached to VCM drop surface energy and coordinates drop dispersion-coalescence preferably, prevents out coarse fodder.
The consumption of high alcoholysis degree, medium viscosity PVA (I) is the 0.001-0.10% of vinyl chloride monomer weight, is preferably 0.01-0.03%;
The consumption of low alcoholysis level, full-bodied PVAC polyvinylalcohol (II) is the 0.001-0.15% of vinyl chloride monomer weight, is preferably 0.04-0.14%;
The consumption of HPMC is the 0.001-0.10% of vinyl chloride monomer weight, is preferably 0.02-0.06%.
Said porosity regulator is selected from the anhydrous sorbitol fatty acid ester, and to use the Span60 effect best, wherein anhydrous sorbitol fatty acid ester hydrophilic and oleophilic value HLB is at 2.0-9.0, preferably 3.0-6.0.After in the above-mentioned porosity regulator adding system, because its oleophilicity is stronger, it is inner that molecular radical infiltrates monomer droplet; Can prevent frequent coalescence between primary particle, eliminate aggregate, can increase the polymerization system oleophilicity simultaneously; Hydrophilic segment in the promotion dispersion agent is to VCM drop internal divergence; And then the epithelium fraction of coverage of reduction resin surface, porosity regulator consumption is the 0.005-0.50% of vinyl chloride monomer weight, is preferably 0.01-0.20%;
Chain-transfer agent is selected from mercaptan compound, trieline, tetracol phenixin and 1-chloro-1-iodoethane etc.; Wherein to adopt mercaptan compound better; Mercaptan compound can be mercaptan type chain transfer agents such as 2 mercapto ethanol, thioglycollic acid-2-ethyl hexyl ester, isooctyl mercaptoacetate, ethylene glycol dimercapto acetate, is best with 2 mercapto ethanol again wherein.The chain-transfer agent consumption is about the 0.001-0.20% of vinyl chloride monomer weight, is preferably 0.005-0.15%.Chain-transfer agent can be before polymerization, once to add; 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;
The PH buffer reagent is selected from sodium hydroxide, sodium hydrogencarbonate, bicarbonate of ammonia etc.; For improving the maximum still ammonium salt class PH buffer reagent of resin sedimentation contribution; Bicarbonate of ammonia preferably, it can improve the resin particle form, stops the generation of resin involucra; Improve the regularity of resin particle, its add-on is so that the PH of reaction system is controlled at 5-8 is advisable;
The water yield and the monomer weight ratio that add are 1.2/1 to 1.8/1, preferably 1.3/1 to 1.5/1, and WOR is too small, and polyreaction occurs unstable, and resin particle distributes and broadens, and a large amount of macrobeads occur and reaches " flake ".The excessive then production efficiency of WOR reduces.
Initiator can be selected organic peroxide initiator or azo-initiator for use; Can be the new enanthic acid tert-butyl ester of peroxo-; The special pentyl ester of peroxo-trimethylacetic acid, peroxide tert pivalate ester, peroxy dicarbonate be two-and in the initiators such as (2-ethylhexyl), ABVN one or more are compound, and its add-on is the 0.01-0.1% of vinyl chloride monomer weight;
Reaction terminating agent is selected from acetone semicarbazone thiocarbamide, dihydroxyphenyl propane, diethyl hydroxylamine or Sodium Nitrite, and its add-on is the 0.005-0.03% of vinyl chloride monomer weight;
Polymeric reaction temperature is controlled at 50 ℃-75 ℃, polymerization temperature decision PVC molecular weight, and polymerization temperature is corresponding to the VCM saturated vapor pressure simultaneously, and polymerization temperature is high more, and polymerization pressure is high more, and too high polymerization temperature has higher requirements to the withstand voltage energy level of polymeric kettle.Polymeric reaction temperature preferably is set in 50 ℃-75 ℃ among the present invention.
The present invention adopts compound dispersing agent, cooperates with certain proportion, adds the porosity regulator of regulating the resin voids rate in addition; Thereby make surperficial epithelium few (discontinuous, local no skin); Loose and porous inner surface and even pore distribution, particle is regular, the polyvinyl chloride resin that plasticizer absorption is high.
When suspension polymerization of VC, vinylchlorid (VCM) drop is scattered in the water through the initiation of initiator and polymerization reaction take place generates polyvinyl chloride resin under stirring action.Dispersant adsorption is in the monomer droplet top layer, plays and disperses and the dual function of protection drop, with stirring dispersion and the merging process that influences the vinylchlorid drop, and performances such as final resin surface epithelium, sedimentation, particle diameter exerted an influence.Through the conversion dispersion system, select suitable dispersion agent proportioning, with the dispersion-Bao glue ability between adjustment water-liquid phase, make the resin of good particle characteristics, low epithelium fraction of coverage, high porosity.
Description of drawings
Fig. 1 is a polyvinyl chloride resin particle surface characteristic (SEM).
Wherein a is embodiment 1 a prepared polyvinyl chloride resin particle characteristics, and b is for adopting the preceding polyvinyl chloride resin particle characteristics of the present invention.After adopting technology of the present invention, resin involucra is less and discontinuous, and the inner particles exposed part is more.
Fig. 2 is a polyvinyl chloride resin granule interior characteristic (SEM).
Wherein c is embodiment 1 a prepared polyvinyl chloride resin particle characteristics, and d is for adopting the preceding polyvinyl chloride resin particle characteristics of the present invention.
After adopting technology of the present invention, the resin particle internal void increases, and agglomeration is less.
Embodiment
Evaluation method:
Among the present invention following method is adopted in the evaluation of resin rerum natura:
The K value
Measuring method according to shown in the GB/T 5761-2006 is measured.
Apparent density
Measuring method according to shown in the GB/T 20022-2005 is measured.
The plasticizer absorption rate
Measuring method according to shown in the GB/T 3400-2002 is measured.
Ageing whiteness
Measuring method according to shown in the GB/T 15595-1995 is measured.
Median size
Adopt FDAC H-7000 transmission electron microscope to measure median size and particle diameter distribution width.
ESEM
Adopt the subsidiary H-7110 sweep attachment of FDAC H-7000 transmission electron microscope that the resin particle form is characterized.
Adopt the high porosity of the above-mentioned method preparation of the present invention, the resin of low epithelium fraction of coverage, resin particle size is controlled easily, is not easy out coarse fodder; The industriallization strong operability; The resin fusion is easy, and is very good to plasticizer absorption, flake is few, has bigger industrializing implementation prospect.
Embodiment 1
Polyreaction is two layers of flat oar in stirring, and bottom insert canal and galvanic couple sleeve pipe are baffle plate, and volume is to carry out in the still of 5L.Processing condition and process are summarized as follows: earlier with 2.1Kg de-salted water, PVA (I) 0.19g, PVA (II) 0.68g, HPMC 0.68g, 0.7g sorbitan monostearate (HLB 4.7), 0.10g 2 mercapto ethanol, 0.5g ABVN, 0.5gNH
4HCO
3Drop in the still, start after the pressure testing and stir, be evacuated to-add VCM 1.4Kg behind the 0.90MPa; Be warming up to 62 ℃ of beginning polymerizations, keep polymerization temperature, add 0.3g diethyl hydroxylamine termination reaction to polymerization pressure decline 0.15MPa; Discharging after pushing back the receipts monomer gets polyvinyl chloride resin behind whiz.
Above dispersion agent PVA (I) is alcoholysis degree 80% (x), the Z 150PH of viscosity 48mPa.s (20 ℃ are measured under 4% concentration); Dispersion agent PVA (II) is alcoholysis degree 45% (x), and viscosity is the Z 150PH of 90mPa.s (25 ℃ are measured under 35% concentration); Dispersion agent HPMC is a methoxyl group substitution value 25%, hydroxypropyl substitution value 6%, the HPMC of viscosity 50mPa.s (20 ℃ are measured under 2% concentration).
Test result is following: K value 57, and apparent density 0.48 (g/ml), the 100g resin plasticizer absorbs 28g, median size 115.0 (μ m), distribution density is 1.15, and its particle characteristics is as shown in Figure 1, and intra slice pattern (SEM) is seen Fig. 2.
Embodiment 2
Change the add-on of dispersion agent PVA (I) into 0.26g, dispersion agent PVA (II) add-on changes 1.60g into, and dispersion agent HPMC add-on changes 0.40g into; Other processing condition are with embodiment 1; Its test result is following: K value 58, and apparent density 0.42 (g/ml), the 100g resin plasticizer absorbs 33g; Median size 110.0 (μ m), distribution density is 1.20.
Embodiment 3
Change the add-on of dispersion agent PVA (I) into 0.22g, dispersion agent PVA (II) add-on changes 1.10g into, and dispersion agent HPMC add-on changes 0.40g into; Other processing condition are with embodiment 1; Its test result is following: K value 57, and apparent density 0.46 (g/ml), the 100g resin plasticizer absorbs 30g; Median size 113.0 (μ m), distribution density is 1.20.
Embodiment 4
Change the add-on of dispersion agent PVA (I) into 0.23g, dispersion agent PVA (II) add-on changes 0.88g into, and dispersion agent HPMC add-on changes 0.41g into; 0.7g sorbitan monostearate, other processing condition are with embodiment 1, its test result is following: K value 57; Apparent density 0.49 (g/ml); The 100g resin plasticizer absorbs 24g, median size 125.0 (μ m), and distribution density is 1.25.
Comparative example 1
Adopting dispersion agent PVA (I) is alcoholysis degree 80% (x), and viscosity is the Z 150PH of 48mPa.s (20 ℃, under the 4% strength of solution condition), does not add PVA (II), does not add the porosity regulator; Other processing condition are with embodiment 1, and test result is following: K value 57, and apparent density 0.53 (g/ml), the 100g resin plasticizer absorbs 20g; Median size 120.0 (μ m), distribution density is 1.15, particle surface has than the pachydermia film; Primary particle is invisible, and the granule interior hole is few, and aggregate is many.
Comparative example 2
When polymerization, do not add the porosity regulator, other processing condition are with embodiment 1.Mensuration result is following: K value 57, and apparent density 0.49 (g/ml), the 100g resin plasticizer absorbs 24g, median size 105.0 (μ m), distribution density is 1.30, and there is bigger hole in granule interior, has big agglomeration, and particle surface has epithelium.
Claims (10)
1. the preparation method of the PVC RESINS of the low epithelium fraction of coverage of a high porosity; It is characterized in that water, vinyl chloride monomer, compound dispersing agent, porosity regulator, chain-transfer agent, PH buffer reagent and initiator are added in the polymeric kettle; Under the pressure of 0.90-1.20MPa, be provided with in the polymerization reaction kettle of whipping appts, carry out polyreaction under 50 ℃-75 ℃; When keeping polymerization temperature to polymerization pressure decline 0.1-0.30MPa; Add reaction terminating agent, discharge the residual chlorine vinyl monomer, from reaction product, collect title product then; Wherein said compound dispersing agent is the Z 150PH of two kinds of partial alcoholysis and the mixture of Vltra tears; The Z 150PH of these two kinds of partial alcoholysis comprises that a kind of alcoholysis degree is Z 150PH I and the low alcoholysis level that a kind of alcoholysis degree is 40-50%, the full-bodied Z 150PH II of 60-120mPa.s of medium viscosity of high alcoholysis degree, the 40-55mPa.s of 70-90%; The consumption of the Z 150PH I of high alcoholysis degree, medium viscosity is the 0.001-0.10% of vinyl chloride monomer weight; The consumption of low alcoholysis level, full-bodied PVAC polyvinylalcohol II is the 0.001-0.15% of vinyl chloride monomer weight, and the consumption of Vltra tears is the 0.001-0.10% of vinyl chloride monomer weight.
2. the preparation method of the PVC RESINS of the low epithelium fraction of coverage of high porosity according to claim 1; The consumption that it is characterized in that the Z 150PH I of high alcoholysis degree, medium viscosity is the 0.01-0.03% of vinyl chloride monomer weight; The consumption of low alcoholysis level, full-bodied PVAC polyvinylalcohol II is the 0.04-0.14% of vinyl chloride monomer weight, and the consumption of Vltra tears is the 0.02-0.06% of vinyl chloride monomer weight.
3. the preparation method of the PVC RESINS of the low epithelium fraction of coverage of high porosity according to claim 1, the methoxy content that it is characterized in that said Vltra tears is 20-40%, hydroxypropyl content 5-15%, viscosity is 30-70mPa.s.
4. the preparation method of the PVC RESINS of the low epithelium fraction of coverage of high porosity according to claim 1, the methoxy content that it is characterized in that said Vltra tears is 25-35%, hydroxypropyl content 5-10%, viscosity is 40-60mPa.s.
5. the preparation method of the PVC RESINS of the low epithelium fraction of coverage of high porosity according to claim 1; It is characterized in that said porosity regulator is selected from the anhydrous sorbitol fatty acid ester; HLB is at 2.0-9.0 for anhydrous sorbitol fatty acid ester hydrophilic and oleophilic value, and porosity regulator consumption is the 0.005-0.50% of vinyl chloride monomer weight.
6. the preparation method of the PVC RESINS of the low epithelium fraction of coverage of high porosity according to claim 1; It is characterized in that chain-transfer agent is selected from mercaptan compound, trieline, tetracol phenixin or 1-chloro-1-iodoethane, the chain-transfer agent consumption is the 0.001-0.20% of vinyl chloride monomer weight.
7. the preparation method of the PVC RESINS of the low epithelium fraction of coverage of high porosity according to claim 6; It is characterized in that chain-transfer agent adopts mercaptan compound, mercaptan compound can be 2 mercapto ethanol, thioglycollic acid-2-ethyl hexyl ester, isooctyl mercaptoacetate or ethylene glycol dimercapto acetate.
8. the preparation method of the PVC RESINS of the low epithelium fraction of coverage of high porosity according to claim 1 is characterized in that said PH buffer reagent is selected from sodium hydroxide, sodium hydrogencarbonate or bicarbonate of ammonia, and its add-on is so that the PH of reaction system is controlled at 5-8 is advisable.
9. the preparation method of the PVC RESINS of the low epithelium fraction of coverage of high porosity according to claim 1 is characterized in that the water yield and the vinyl chloride monomer weight ratio that add are 1.2/1 to 1.8/1.
10. the preparation method of the PVC RESINS of the low epithelium fraction of coverage of high porosity according to claim 1; It is characterized in that initiator selects organic peroxide initiator or azo-initiator for use; Its add-on is the 0.01-0.1% of vinyl chloride monomer weight; Reaction terminating agent is selected from acetone semicarbazone thiocarbamide, dihydroxyphenyl propane, diethyl hydroxylamine or Sodium Nitrite, and its add-on is the 0.005-0.03% of vinyl chloride monomer weight.
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| CN104710550A (en) * | 2013-12-11 | 2015-06-17 | 浙江蓝天环保高科技股份有限公司 | High molecular weight polyvinylidene fluoride resin and preparation method thereof |
| CN106554444A (en) * | 2015-09-28 | 2017-04-05 | 中国石油化工股份有限公司 | The preparation method of ultra low polymerization degree polyvinyl chloride resin solution |
| CN106749795A (en) * | 2016-07-17 | 2017-05-31 | 佛山瑞箭体育器材有限公司 | A kind of preparation method of Corvic |
| CN106749793A (en) * | 2016-04-23 | 2017-05-31 | 佛山瑞箭体育器材有限公司 | A kind of preparation method of Corvic |
| CN107151280A (en) * | 2017-04-26 | 2017-09-12 | 安徽华塑股份有限公司 | A kind of suspension method prepares the synthesis technique of polyvinyl chloride |
| CN108192001A (en) * | 2017-12-26 | 2018-06-22 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | A kind of preparation method of polyvinyl chloride resin used for chlorination |
| CN108976335A (en) * | 2017-05-31 | 2018-12-11 | 中国石油化工股份有限公司 | A kind of production method of high porosity polyvinyl chloride resin |
| CN109384874A (en) * | 2017-08-02 | 2019-02-26 | 中国石油化工股份有限公司 | A kind of epithelium remover and polymerization improving Corvic porosity |
| CN110724215A (en) * | 2018-07-16 | 2020-01-24 | 中国石油化工股份有限公司 | Preparation method of low-film PVC (polyvinyl chloride) resin |
| CN112189023A (en) * | 2018-10-29 | 2021-01-05 | 株式会社Lg化学 | Vinyl chloride-based polymer and method for preparing same |
| CN113651910A (en) * | 2021-09-15 | 2021-11-16 | 金川集团股份有限公司 | Preparation method of large-particle-size narrow-distribution polyvinyl chloride resin |
| CN115449003A (en) * | 2021-06-09 | 2022-12-09 | 中国石油化工股份有限公司 | Preparation method of PVC resin with low involucra content and uniform pores |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4775702A (en) * | 1987-04-14 | 1988-10-04 | The B. F. Goodrich Company | Inversion process for producing low-skin porous friable particles of crosslinked PVC resin |
| CN1330089A (en) * | 2001-08-07 | 2002-01-09 | 上海氯碱化工股份有限公司 | Application of novel dispersion system in preparing polyvinyl chloride resin dedicated for pipes with high apparent density |
| CN1927898A (en) * | 2006-09-13 | 2007-03-14 | 上海氯碱化工股份有限公司 | Preparation method of low polymerization degree and high porosity resin |
-
2010
- 2010-10-22 CN CN2010105151781A patent/CN102453176A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4775702A (en) * | 1987-04-14 | 1988-10-04 | The B. F. Goodrich Company | Inversion process for producing low-skin porous friable particles of crosslinked PVC resin |
| CN1330089A (en) * | 2001-08-07 | 2002-01-09 | 上海氯碱化工股份有限公司 | Application of novel dispersion system in preparing polyvinyl chloride resin dedicated for pipes with high apparent density |
| CN1927898A (en) * | 2006-09-13 | 2007-03-14 | 上海氯碱化工股份有限公司 | Preparation method of low polymerization degree and high porosity resin |
Cited By (16)
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|---|---|---|---|---|
| CN104710550A (en) * | 2013-12-11 | 2015-06-17 | 浙江蓝天环保高科技股份有限公司 | High molecular weight polyvinylidene fluoride resin and preparation method thereof |
| CN106554444A (en) * | 2015-09-28 | 2017-04-05 | 中国石油化工股份有限公司 | The preparation method of ultra low polymerization degree polyvinyl chloride resin solution |
| CN106749793A (en) * | 2016-04-23 | 2017-05-31 | 佛山瑞箭体育器材有限公司 | A kind of preparation method of Corvic |
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| CN108192001A (en) * | 2017-12-26 | 2018-06-22 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | A kind of preparation method of polyvinyl chloride resin used for chlorination |
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| CN112189023A (en) * | 2018-10-29 | 2021-01-05 | 株式会社Lg化学 | Vinyl chloride-based polymer and method for preparing same |
| US11773194B2 (en) | 2018-10-29 | 2023-10-03 | Lg Chem, Ltd. | Vinyl chloride-based polymer and method for preparing same |
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