CN1256279A - Synthesis of transparnt shock-resisting modifier - Google Patents
Synthesis of transparnt shock-resisting modifier Download PDFInfo
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- CN1256279A CN1256279A CN 98122122 CN98122122A CN1256279A CN 1256279 A CN1256279 A CN 1256279A CN 98122122 CN98122122 CN 98122122 CN 98122122 A CN98122122 A CN 98122122A CN 1256279 A CN1256279 A CN 1256279A
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Abstract
During the synthesis, small size butadiene styrene latex is first synthesized and then used as seeds and enlarged by emulsion polymerization of the copolymerized component of bytadiene and styrene. After that, grafting polymerization is effected in the latex through two steps. The method of the present invention can improve the stability of the polymerization system, raise the solid content of grafted latex. The synthesized modified butadiene styrene resin, when mixed with PVC, can raise its shock resistance, maintains excellent yellow index, aging performance and transparency.
Description
The present invention relates to the synthetic method of a kind of polyvinyl-chloride use transparnt shock-resisting modifier divinyl, vinylbenzene, methyl methacrylate copolymer (being called for short the MBS resin).
The MBS resin is a synthetic novel high polymer material under the particle design notion, has typical nucleocapsid structure on submicroscopic form.When being subjected to external impacts, its core, a diameter can change form at the spherical core of the rubber phase of 50～300nm, and absorbing and disperseing impact energy, outside is the shell that vinylbenzene and methyl methacrylate-grafted form.Because its solubility parameters and PVC are approaching, play the effect of bonding interface agent behind the shell partial melting between PVC and rubber phase particle, form homogeneous phase in the processing mixing process, rubber phase then is dispersed in the PVC continuum with particle state.Through the resin modified PVC of MBS, not only under the prerequisite of the harmless transparency, improved shock resistance, and further improved the winter hardiness and the processing fluidity of goods, thereby its application is very widely.
Yet, with regard to the modification of polyvinyl chloride resin, want not lose the transparency and the stress whiting performance of PVC excellence, require synthesize MBS resin particle particle diameter can not be too big, not influence seeing through of visible light, cause the scattering of light; And the prerequisite that obtains better shock resistance is to have an enough big particle diameter, and with abundant absorption and stop passing through of impact energy, thereby the transparency and shock resistance are two conflicting notions.How to coordinate two kinds of performances of mechanics and optics, prepare MBS resin transparent and that anti-impact is all good is the focus of this area research and development always.
As everyone knows, transparent and anti-impact of the preparation key that has both type MBS resin is the styrene-butadiene latex (SBRL) of synthetic suitable particle diameter.Yet usually through the SBRL of step emulsion polymerization preparation, its particle diameter all less (about 30～70nm), therefore need to adopt suitable technology that particle diameter is increased.Patent report about SBRL hole enlargement aspect is more.The flat 5-262945 of open patent of Japan Zhong Yuan company has introduced among the USP 4287312 of Wu Yu company carrying out hole enlargement in the water-soluble ionogen adding small particle size styrene-butadiene latex, carries out the method for graft polymerization then, its first-selected hole enlargement agent is NaCl, KCl, hydrochloric acid, acetic acid etc.Its goods have better comprehensive performance, weak point is the polymerization system instability, easily produces blob of viscose in the polymerization process, and all there is certain difficulty in the raising of transformation efficiency, solid content in the reaction process, and the introducing of hole enlargement agent can cause corrosion to equipment installation undoubtedly, is inapplicable therefore.And the European patent EP 0144081 of Japanese MITSUBISHI RAYON company application, the clear 60-112811 of EP 77038 and Japanese Patent, and the EP 62901 of the German BASF AG technology that all adopted carboxylic acid copolymer hole enlargement agent latex to carry out hole enlargement.Its difference is that preceding two pieces of patents all adopt the adding ionogen to make the hole enlargement system stable after hole enlargement finishes, and then adds the stability that emulsifying agent guarantees the graft polymerization system.The particle diameter of graft polymer latex is diminished, size distribution by bimodal become unimodal, thereby influence its impact-resistance, second can make final MBS resin smell big, particle is meticulous, influences operating environment.Then two pieces of patents are then emphasized to have added the esters of acrylic acid component for anti-impact and the thermotolerance of improving the finished product in the butylbenzene polymerization process, and ignored very important when adopting hole enlargement agent latex to increase a particle diameter problem, promptly how to solve the problem of polymerization system stability.In addition, the common problem of above-mentioned four pieces of patents be selected expanding technology all in various degree influence the transparency and the yellowness index of MBS/PVC blend, cause the limitation of its Application Areas.Though Japan Zhong Yuan company has also adopted the operational path of seeding polymerization at Chinese patents CN 85104049A, but in the component that its grafting order of addition(of ingredients) is a grafting to add mainly is methyl methacrylate, account for 90～100% (weight percents of total amount, down together), in the component that secondary grafting adds mainly is vinylbenzene, accounts for 90～100% of total amount.When adopting grafting like this in proper order, can produce infringement to the polyvinyl chloride resin inherent transparency, and certain influence be arranged for processing plasticizing.And when outer grafting methyl methacrylate, because its solubility parameters is more close with PVC with refractive index, processing mixing process in the easier fusion of PVC, between PVC and rubber phase particle, play the effect of bonding interface agent, more help keeping the transparency of PVC excellence and promote the even processing plasticizing of two-phase.Thereby the grafting order adjusted be necessary.
Purpose of the present invention is exactly in order to solve the weak point of prior art, a kind of novel process of synthetic transparnt shock-resisting modifier is provided, make the synthetic MBS of institute resin guarantee polymerization system stability, and under the prerequisite of harmless polyvinyl chloride resin excellent transparency, improve shock resistance and yellowness index to greatest extent.
For achieving the above object, technical scheme of the present invention is the styrene-butadiene latex that at first synthesizes small particle size, carry out two step letex polymerizations with this latex as seed afterwards, make the styrene-butadiene latex of particle diameter about 100nm, carry out graft polymerization then in two steps, the first step grafting is based on vinylbenzene, be mixed with the monomer mixture of a small amount of methyl methacrylate, the remaining methyl methacrylate of the second step grafting, last cohesion and drying process routinely carries out aftertreatment, makes the MBS resin.Through the PVC of this modification, not only shock resistance and properties of transparency excellence, and keep ageing-resistant performance preferably, yellowness index and processing plasticizing performance.Details are as follows for its preparation process:
The first step, synthetic small particle size styrene-butadiene latex (following per-cent and percentage composition all are weight percentage and weight percentage if no special instructions)
The common emulsion polymerization of synthetic employing of styrene-butadiene latex.In order to satisfy the requirement of shock resistance, the content of divinyl is generally 70～90% in the styrene-butadiene latex, and vinylbenzene is 30～10%.Initiator can be used the persulfuric acid salt as Potassium Persulphate or ammonium persulphate etc., it perhaps is oxygenant with the di-isopropylbenzene hydroperoxide, rongalite, b diammonium disodium edta salt and ferrous sulfate are the oxidation-reduction trigger system of reductive agent, and its consumption is generally 0.3～0.6% of monomer consumption.Emulsifying agent can be selected from potassium oleate, potassium stearate, nilox resin acid potassium or their compound system, but this must possess two conditions: the one, and can make reaction system stable; The 2nd, have good thermotolerance, be unlikely to variable color in the course of processing and influence the color and luster of product.The emulsifying agent consumption is very few, can influence the stability of polymerization system, produces a large amount of blob of viscoses; The emulsifying agent consumption is too much, can cause product whiteness to descend again, so the consumption of emulsifying agent is good with 3～5% of monomer weight.In addition, molecular weight and gel content in order to control styrene-butadiene latex better also need add molecular weight regulator and linking agent in the polymerization process, the former generally uses thio-alcohol, as just or tert-dodecyl mercaptan, its add-on is generally 0.1～1.0% of monomer consumption, and preferably 0.3～0.6%; The latter is general with unsaturated polyfunctional group component, as divinylbenzene (DVB), and Ethylene glycol dimethacrylate (EGDM), triallyl cyanurate (CTA) etc., divinylbenzene preferably, its consumption is generally 1～10% of monomer consumption, preferably between 1.5～3.0%.The middle control index of synthetic styrene-butadiene latex be: particle diameter 40～60nm, gel content 85～95%, transformation efficiency 95～100%, solid content 30～40% (all adopting conventional method of analysis to measure).
Second step, the styrene-butadiene latex of the synthetic suitable particle diameter of seeding polymerization method
The synthetic process implementing that still adopts the high pressure letex polymerization of the styrene-butadiene latex of suitable particle diameter.Selected monomer comprises divinyl, vinylbenzene and other component of copolymerization with it.For preparing the product of different impact properties, seed latex and monomeric ratio can be between 1: 20～20: 1.Latex/monomer when too high or too low, all can make the particle diameter of synthetic styrene-butadiene latex improper, thereby the improvement of impact performance is undesirable.In addition, consider the possibility that subsequent technique is implemented, generally selecting seed latex and monomeric ratio is 1: 20～5: 1, preferably between 1: 20～1: 1.Selected comonomer ratio, emulsifying agent, initiator, kind and consumption selected in the kind of molecular weight regulator and linking agent and consumption and the small particle size styrene-butadiene latex building-up process are identical.What need particularly point out is, for size and the distribution of controlling latex particle size better, the consumption of emulsifying agent should be controlled between 0～3%, preferably 0.5～1.5%.The middle control index of synthetic styrene-butadiene latex as follows: particle diameter 80～150nm, gel content 85～95%, transformation efficiency 93～98%, solid content 30～40% (all adopting conventional method of analysis to measure).
The 3rd step, graft latex synthetic
Adopt emulsion polymerization to carry out the synthetic of graft latex.After at first the styrene-butadiene latex of above-mentioned suitable particle diameter being risen to predetermined temperature of reaction, the vinylbenzene that adds whole formula ratios, linking agent, tert-dodecyl mercaptan and a spot of methyl methacrylate carry out a graft polymerization, and initiator can be selected the persulfuric acid salt as Potassium Persulphate, ammonium persulphate etc. for use; Also optionally make oxygenant in order to superoxide such as di-isopropylbenzene hydroperoxide, cumyl hydrogen peroxide, ferrous sulfate, b diammonium disodium edta salt (EDTA), rongalite are made the oxidation-reduction trigger system of reductive agent, and its add-on is generally 0.4～0.8% of a grafted monomer total amount.After a grafting meets the requirements, add remaining methyl methacrylate and corresponding component carries out secondary grafting, wherein the consumption of initiator is similarly 0.4～0.8% of monomer total amount, to the latex of secondary grafting index up to specification.
In the MBS of above-mentioned preparation resin graft latex, add 0.5～1.0% oxidation inhibitor, as commercially available oxidation inhibitor β-positive 18 carbon esters (antioxidant 1076) of (4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid, Tyox B (oxidation inhibitor DLTDP) etc.With dilute sulphuric acid or dilute hydrochloric acid cohesion,, obtain the MBS rosin products after the drying then through washing.
If necessary, for improving resin color and luster and processing plasticizing performance, also can in the graft polymerization process, add unsaturated cyanogen class monomer or long-chain (methyl) alkyl-acrylates component, as vinyl cyanide, methacrylonitrile, acrylic acid methyl esters, ethyl ester or butyl ester, and the methyl esters of methacrylic acid, ethyl ester or butyl ester etc.
Will be by after the inventive method synthetic MBS resin and the PVC blend, make the print of 1mm and 3mm respectively, according to the described method test of ASTM D-256 shock strength, according to described method test transparency of GB 2410-80 and turbidity, measure thermostability according to the described method of GB 1035-70, according to the described method test of GB 2409-80 yellowness index, the test of polymerization system stability is recently weighed according to the percentage that gel quantity accounts for total dried glue amount, the measuring method of gel quantity be latex after reaction is finished with 100 order stainless steel sift net filtrations, leach the weight of thing and per-cent that the gel quantity sum in the polymeric kettle accounts for polymer dry glue gross weight and be the percentage gel quantity.
In order to describe technical characterstic of the present invention better, the spy enumerates following each embodiment, but the present invention is not limited to each embodiment, if do not run counter to design of the present invention, the various changes of being done still belong to category of the present invention.Embodiment 1
(1) small particle size styrene-butadiene latex A's is synthetic
In the autoclave of agitator is housed, add each material in following ratio:
75 parts of divinyl
25 parts of vinylbenzene
3.5 parts of potassium oleates
0.5 part of potassium stearate
0.65 part in Repone K
0.5 part of Potassium Persulphate
0.5 part of tert-dodecyl mercaptan
2.5 parts of divinylbenzenes
180 parts in water is opened and is stirred and with twice back intensification of nitrogen replacement, and constant temperature and stirred polymerization 9 hours to the temperature of reaction obtains that a kind of to have transformation efficiency be 95%, and median size is the styrene-butadiene latex (being referred to as latex A) of 41nm.
(2) the styrene-butadiene latex B's of suitable particle diameter is synthetic
Selecting seed latex and the monomeric weight ratio of copolymerization is 1: 9.In the autoclave of agitator is housed, add each material by following prescription:
11.1 parts of latex A
75 parts of divinyl
25 parts of vinylbenzene
0.875 part of potassium oleate
0.125 part of potassium stearate
0.65 part in Repone K
0.5 part of Potassium Persulphate
0.5 part of tert-dodecyl mercaptan
2.5 parts of divinylbenzenes
180 parts of unlatchings of water are stirred and are heated up with twice back of nitrogen replacement, constant temperature and stirred polymerization 9～10 hours to the temperature of reaction, obtain that a kind of to have transformation efficiency be 95.2%, median size is the styrene-butadiene latex (being referred to as latex B) of 102nm.
(3) graft latex is synthetic
Following each component is added in the polymerization under atmospheric pressure still that has stirring successively:
60.0 parts of latex B (weight by dry rubber)
20.9 parts of vinylbenzene
6.4 parts of methyl methacrylates
0.137 part of tert-dodecyl mercaptan
0.683 part of divinylbenzene
Water is opened stirring and is warmed up to 62 ± 2 ℃ for 300 part, adds following oxidation-reduction trigger system then:
0.137 part of di-isopropylbenzene hydroperoxide
0.205 part of rongalite
0.005 part of b diammonium disodium edta salt (EDTA)
0.002 part of polyreaction of ferrous sulfate is after 4 hours, and measuring transformation efficiency is 95.6%, adds following each component then and carry out secondary grafting in reactor:
12.8 parts of methyl methacrylates
0.064 part of tert-dodecyl mercaptan
Divinylbenzene stirs after 5 minutes for 0.256 part, adds following oxidation-reduction trigger system:
0.064 part of di-isopropylbenzene hydroperoxide
0.096 part of rongalite
0.002 part of b diammonium disodium edta salt (EDTA)
Ferrous sulfate continues polyreaction after 3 hours for 0.001 part, obtains MBS resin latex (being referred to as latex C).Measuring transformation efficiency is 97.8%, and particle diameter is 110nm.
(4) aftertreatment of MBS latex and processed and applied test
In the above-mentioned 100 parts of latex C (weight by dry rubber) that obtain, add with 0.7 part of potassium stearate emulsive antioxidant 1076,0.4 part of DLTDP, condense with dilute sulphuric acid then, dry under 60 ℃ after the centrifuge dehydration, obtain the MBS rosin products, detect through electron microscope, the particle that wherein is not more than 50nm is respectively 7%, 5% (volume percent) with the proportion of particles that is not less than 150nm.
According to a conventional method under 185 ℃, on open mixing roll mixing 3 minutes, under 180 ℃, compacting was 5 minutes on the compression molding instrument, makes the thick print of 1mm and 3mm respectively then with following each component:
100 parts of PVC (TK-800)
7 parts of MBS
0.5 part of lubricant G-74 (commercially available)
3 parts of stablizers 890 (commercially available)
The thick print of 3mm is pressed the shock strength that ASTM D-256 method is measured print, the thick print of 1mm is pressed GB2410-80 measure transparency and turbidity, press the thermostability of the method test MBS resin of GB 1035-70, press the yellowness index of the method test MBS resin of GB 2409-80, its The performance test results sees Table 1.Embodiment 2
In the process of the synthetic small particle size styrene-butadiene latex of the foregoing description 1, change the add-on of potassium oleate and potassium stearate into 3 parts and 0.3 part respectively, making transformation efficiency is 93%, the styrene-butadiene latex of particle diameter 52nm.In the building-up process of polymerization formula latex B, changed the ratio of seed latex A and divinyl, styrene monomer into 1: 5 by original 1: 9, all the other and embodiment 1 are identical.Its The performance test results sees Table 1, detects through electron microscope, and the particle that wherein is not more than 50nm is respectively 6.5%, 5.8% (volume percent) with the particle proportion that is not less than 150nm.Embodiment 3
In the building-up process of the foregoing description 1 polymerization formula latex B, changed the ratio of seed latex A and divinyl, styrene monomer into 1: 15 by original 1: 9, all the other and embodiment 1 are identical.Its The performance test results sees Table 1.Embodiment 4
In the building-up process of the foregoing description 1 polymerization formula latex C, change the water yield in the grafting process into 180 parts by original 300 parts, all the other and embodiment 1 are identical.The solid content of gained MBS latex is 35%, and its The performance test results sees Table 1.Embodiment 5
In the building-up process of the foregoing description 1 polymerization formula latex A, B, the divinyl during comonomer formed: vinylbenzene changed 90: 10 into by original 75: 25, and all the other and embodiment 1 are identical.Its The performance test results sees Table 1.Comparative example 1
In the foregoing description 1 polymerization formula building-up process, the preparation process of seeding polymerization part latex B is removed, all the other and embodiment 1 are identical.Its The performance test results sees Table 1.Comparative example 2
In the building-up process of the foregoing description 1 polymerization formula, the preparation process of seeding polymerization part latex B is removed, change into inorganic salt (NaCl) as the hole enlargement agent, be 100nm with styrene-butadiene latex A hole enlargement to the particle diameter of small particle size, all the other and embodiment 1 are identical.Its The performance test results sees Table 1.Comparative example 3
In the building-up process of the foregoing description 1 polymerization formula, the preparation process of seeding polymerization part latex B is removed, change into weak acid (acetic acid) as the hole enlargement agent, be 100nm with styrene-butadiene latex A hole enlargement to the particle diameter of small particle size, all the other and embodiment 1 are identical.Its The performance test results sees Table 1.Comparative example 4
In the building-up process of the foregoing description 1 polymerization formula, the preparation process of seeding polymerization part latex B is changed into butyl acrylate-Sipacril 2739OF latex as the hole enlargement agent the styrene-butadiene latex hole enlargement of small particle size to 100nm, and all the other and embodiment 1 are identical.Its The performance test results sees Table 1.Comparative example 5
In the building-up process of the foregoing description 1 polymerization formula latex C, the order of addition(of ingredients) of grafting process is adjusted, change grafting methyl methacrylate and corresponding additive and oxidation-reduction trigger system, secondary grafting vinylbenzene and corresponding additive and oxidation-reduction trigger system into by original addition step.All the other and embodiment 1 are identical.Its The performance test results sees Table 1.
Table 1
| Test number | Seed latex particle diameter (nm) | Gel quantity *(％) | Shock strength (J/m) | Transparency (%) | Turbidity (%) | Yellowness index **????(YI) | The processing plasticizing performance *** |
| Embodiment 1 | ??102 | ??0.03 | ????119.4 | ????87.6 | ????3.9 | ????-2.15 | ????●●●● |
| Embodiment 2 | ??101 | ??0.02 | ????116.8 | ????87.6 | ????3.4 | ????-2.44 | ????●●●● |
| Embodiment 3 | ??105 | ??0.02 | ????117.8 | ????87.4 | ????3.6 | ????-2.34 | ????●●●● |
| Embodiment 4 | ??102 | ??0.06 | ????117.2 | ????88.3 | ????4.1 | ????-1.97 | ????●●●● |
| Embodiment 5 | ??102 | ??0.05 | ????123.7 | ????86.7 | ????4.7 | ????-1.58 | ????●●●● |
| Comparative example 1 | ???43 | ??0.01 | ?????78.5 | ????88.4 | ????3.2 | ????-1.88 | ???●●●●● |
| Comparative example 2 | ??109 | ??1.89 | ????106.3 | ????88.1 | ????5.7 | ????2.32 | ?????●●● |
| Comparative example 3 | ??100 | ??1.75 | ????102.1 | ????87.5 | ????6.4 | ????2.46 | ?????●●● |
| Comparative example 4 | ??100 | ??2.87 | ????124.6 | ????87.3 | ???12.9 | ????7.98 | ??????●● |
| Comparative example 5 | ??102 | ??0.21 | ????115.8 | ????87.8 | ????6.6 | ????1.24 | ????●●●● |
Annotate: the situation of the height reflection polymerization system stability of * gel quantity numerical value; * yellowness index (YELLOW INDEX) be with the certain criteria blank as object of reference, survey
The order of excellence of the * * * processing plasticizing performance that the yellowness index of print and the difference of marker embody is as follows: ● ● ● ● ●＞● ● ● ●＞● ● ●＞● ●＞●.
Claims (5)
- The synthetic method of 1 one kinds of transparent double high shock resistance type modifying agent divinyl of used for polyvinyl-chloride resin, vinylbenzene, methyl methacrylate ternary graft copolymer, comprising: A is at first by divinyl and the styrene copolymerized small particle size styrene-butadiene latex that makes; B as seed, carries out seeding polymerization by copolymerization divinyl and vinylbenzene component with the latex of steps A gained on this latex, make the styrene-butadiene latex of suitable particle diameter; C is grafted to vinylbenzene and methyl methacrylate on the latex that step B makes in two steps, forms a kind of ternary graft copolymer MBS resin.
- 2 by the described method of claim 1, and the median size that it is characterized in that the styrene-butadiene latex that steps A makes is 40～60nm.
- 3 by the described method of claim 1, and the median size that it is characterized in that the styrene-butadiene latex that step B makes is 100～110nm, and the particle that wherein is not more than 50nm all is no more than 10% (volume percent) with the shared per-cent of particle that is not less than 150nm.
- 4 by the described method of claim 1, it is characterized in that the weight ratio of seed latex and divinyl in the seeding polymerization process, styrene monomer is 1: 20～20: 1.
- 5 by the described method of claim 1, and the solid content that it is characterized in that institute's synthetic graft latex reaches 30% can keep the stable and excellent performance of system preferably when above.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100473680C (en) * | 2003-08-02 | 2009-04-01 | Lg化学株式会社 | Acryl-silicone hybrid impact modifiers and method for preparing the same and vinyl chloride resin compositions having the same |
| CN101191001B (en) * | 2006-11-18 | 2010-08-11 | 山东瑞丰高分子材料股份有限公司 | Transparent MBS resin composition with excellent processing property |
| CN101418060B (en) * | 2007-10-23 | 2010-09-29 | 山东瑞丰高分子材料股份有限公司 | AS resin with excellent impact resistance property |
| CN102863726A (en) * | 2011-07-04 | 2013-01-09 | 中国石油化工股份有限公司 | Synthetic method of PVC modifier |
| CN107602769A (en) * | 2017-09-20 | 2018-01-19 | 山东鼎鼎化学科技股份有限公司 | A kind of method of synthesis MBS resins |
| CN108997534A (en) * | 2018-09-06 | 2018-12-14 | 万达集团股份有限公司 | A kind of preparation method of low-temperature transparent high-impact MBS resin |
| CN112759714A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Preparation method of high-toughness graft copolymer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1046539C (en) * | 1995-04-27 | 1999-11-17 | 中国石化齐鲁石油化工公司 | Synthesis method of polyvinyl chloride impact modifier being butadiene, styrene, methyl methacrylate copolymer |
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- 1998-12-07 CN CN98122122A patent/CN1114635C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100473680C (en) * | 2003-08-02 | 2009-04-01 | Lg化学株式会社 | Acryl-silicone hybrid impact modifiers and method for preparing the same and vinyl chloride resin compositions having the same |
| CN101191001B (en) * | 2006-11-18 | 2010-08-11 | 山东瑞丰高分子材料股份有限公司 | Transparent MBS resin composition with excellent processing property |
| CN101418060B (en) * | 2007-10-23 | 2010-09-29 | 山东瑞丰高分子材料股份有限公司 | AS resin with excellent impact resistance property |
| CN102863726A (en) * | 2011-07-04 | 2013-01-09 | 中国石油化工股份有限公司 | Synthetic method of PVC modifier |
| CN102863726B (en) * | 2011-07-04 | 2016-04-13 | 中国石油化工股份有限公司 | The synthetic method of PVC modifier |
| CN107602769A (en) * | 2017-09-20 | 2018-01-19 | 山东鼎鼎化学科技股份有限公司 | A kind of method of synthesis MBS resins |
| CN108997534A (en) * | 2018-09-06 | 2018-12-14 | 万达集团股份有限公司 | A kind of preparation method of low-temperature transparent high-impact MBS resin |
| CN112759714A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Preparation method of high-toughness graft copolymer |
| CN112759714B (en) * | 2019-10-21 | 2022-08-12 | 中国石油化工股份有限公司 | Preparation method of high-toughness graft copolymer |
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