CN101177469A - Preparation of polynuclear layer impulse modifier having whole core-shell structure - Google Patents
Preparation of polynuclear layer impulse modifier having whole core-shell structure Download PDFInfo
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- CN101177469A CN101177469A CNA2007100311000A CN200710031100A CN101177469A CN 101177469 A CN101177469 A CN 101177469A CN A2007100311000 A CNA2007100311000 A CN A2007100311000A CN 200710031100 A CN200710031100 A CN 200710031100A CN 101177469 A CN101177469 A CN 101177469A
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Abstract
The utility model discloses a preparation method for a multi-nuclear-layer shock proof modifying agent with an integrated core-shell structure. Butyl methacrylate or ethyl acrylate is used as the monomer, N, N' - methylene-bisacrylamide is used as the cross linker, potassium sulfate is used as the initiator, compound emulsifier is adopted as a steady system, to prepare the seed latex; based on the seed latex, a nuclear layer with a low vitrification transition temperature is prepared by means of the craft of two-step nucleation; during the later stage of the first nuclear layer reaction, the second nuclear layer is prepared by means of the graft copolymerization; during the later stage of the second nuclear layer preparation, a casing with a high vitrification transition temperature is prepared by means of the graft copolymerization; after full reaction, a multi-nuclear-layer shock proof modifying agent with an integrated core-shell structure is obtained after the spray-drying; compared with the ordinary core-shell shock proof modifying agent with the similar components, the utility model has improved anti-impact performance by more than 10%.
Description
Technical field
The present invention relates to a kind of preparation with multinuclear layer anti-impact modifier of complete nucleocapsid structure.
Background technology
Polyvinyl chloride (PVC) is widely used in numerous areas such as construction and decoration, household electrical appliance, toy as one of three big general-purpose plastics.But owing to well-known reason, PVC but simultaneously all exist many defectives at aspects such as resistance to impact shock, weather resistances, the CPE that adopt carry out the modification of shock resistance and weather resistance more in the present domestic PVC goods, it is advantageous that the low production technology of price is ripe.But CPE exists serious defectives such as work range is narrow, anti-uv-ray is poor (weather resistance is poor), finish size poor stability, anti-low temperature ball falling impact ability simultaneously, be restricted when especially using, can't produce high-quality product as the outdoor section bar of PVC-U.Use more MBS anti-impact modifier (as the multipolymer of butadiene-styrene-methyl methacrylate) in addition because it is less to the influence of plastics properties of transparency, and shock resistance better obtains certain application.Because the wherein existence of divinyl makes its weather resistance poor, outdoor use descends its shock resistance rapidly, so its goods can only indoors use.
And ACR not only has excellent shock resistance, also have excellent weather resistance simultaneously and promote plasticizing capacity, can be widely used in various soft or hard PVC plastics and the indoor outer PVC plastics, can improve the various performance index of goods greatly, be the outstanding anti-impact modifier product of generally acknowledging both at home and abroad at present.
With regard to present ACR preparation technology, generally be to use the main component of the lower butyl polyacrylate of second-order transition temperature (BA) as stratum nucleare, use second-order transition temperature higher, with PVC have excellent compatibility can polymethylmethacrylate (MMA) as the shell main component, adopt the synthesis technique of emulsion graft copolymerization to obtain hud typed multipolymer.But in actual production process because the differences such as consistency of stratum nucleare and shell monomers, often cause the finished product can't obtain complete kernel shell parcel shape structure, promptly can not form complete soft nuclear monocoque, or the nucleocapsid structure that obtains is stable inadequately, to add man-hour destroyed easily being used for the PVC goods, the result often makes a large amount of kernels exposed, because kernel rubber phase and PVC compatibility performance are poor, cause in the plastics course of processing, impact property reduces, and consistency is poor, the easy weather stain of PVC phase high temperature, the roll banding phenomenon appears in the course of processing, is reflected to goods and flavescence then occurs, defectives such as thermal stability variation.
Chinese patent 03800162.4 adopts a kind of multi-step emulsion polymerization method, and purpose provides a kind of rubbery kernel particle, safeguards its impact resistance by the control swelling index.Chinese patent 200610112208.8 has been introduced the preparation method that a kind of nucleocapsid structure polyvinyl chloride impact with transition layer hits properties-correcting agent, adopt seed emulsion polymerization, in seed emulsion, introduce n-butyl acrylate as stratum nucleare (being so-called transition layer), introduce vinylchlorid as shell, obtain a kind of core-shell copolymerized thing.
Summary of the invention
At the problem on the above-mentioned ACR synthetic technology, the invention provides a kind of preparation method with multinuclear layer anti-impact modifier of complete nucleocapsid structure, the preparation of this properties-correcting agent with butyl methacrylate or ethyl propenoate as monomer, N, N '-methylene-bisacrylamide is as linking agent, Potassium Persulphate (KPS) is as initiator, adopt Sodium dodecylbenzene sulfonate (LAS)/sodium lauryl sulphate (SLS)/class of department 60 (SP-60)/polyoxyethylene nonylphenol ether (NP-70) compound emulsifying agents, the preparation seed latex; On the seed latex basis, by the stratum nucleare that two step nucleation prepared have low glass bricking temperature, the preparation of first stratum nucleare is monomer with the butyl methacrylate, N, and N '-methylene-bisacrylamide and homemade molecular formula are C
4H
9OOC=CHRCH=CHCOOCH
2(R is main chain C to R '
3～C
8Alkyl, R ' is-C
3H
7) bifunctional compound form multiple crosslinking agent, Potassium Persulphate (KPS) is as initiator; In the later stage of the first stratum nucleare preparation feedback, prepare second stratum nucleare by graft copolymerization, the preparation of second stratum nucleare is a monomer with butyl methacrylate, vinylbenzene, homemade molecular formula is C
4H
9OOC=CHRCH=CHCOOCH
2(R is main chain C to R '
3～C
8Alkyl, R ' is-H) bifunctional compound and Vinylstyrene form multiple crosslinking agent, Potassium Persulphate (KPS) is as initiator; In the later stage of second stratum nucleare preparation, prepare shell by graft copolymerization with high glass-transition temperature, shell is a monomer with methyl methacrylate, vinylbenzene, homemade molecular formula is C
4H
9OOC=CHRCH=CHCOOCH
2(R is main chain C to R '
3～C
8Alkyl, R ' is-H) bifunctional compound and Vinylstyrene form multiple crosslinking agent, Potassium Persulphate (KPS) is as initiator.After reacting completely, the spray-dried multinuclear layer anti-impact modifier that obtains having complete nucleocapsid structure.Be connected with shell with first stratum nucleare by chemical bond, not only on performance, between first stratum nucleare and shell, play transition and transfer function, the formation of chemical bond has guaranteed the stability of nucleocapsid structure between nucleocapsid simultaneously, thereby obtains the anti-impact modifier synthesis technique of complete nucleocapsid structure.The complete nucleocapsid structure multinuclear layer impact modifying agent that heat analysis obtains preparing under the condition of the present invention has three glass transition temperature Tg, be respectively-32～-14 ℃, 21 ℃～-32 ℃ and 94 ℃～-110 ℃, correspond respectively to first stratum nucleare, second stratum nucleare and shell.
Particular content of the present invention and step are as follows:
The first step: seed latex preparation, monomer are a kind of in butyl methacrylate or the ethyl propenoate, and monomer mass is 5～15% of a prepared anti-impact modifier quality, and the mass content of monomer in reaction system is 2～10%.Initiator potassium persulfate (KPS) consumption is 0.1～0.8% of a monomer mass, and linking agent is N, and N '-methylene-bisacrylamide, consumption are 0.01～0.1% of monomer mass.Compound emulsifying agent proportioning (quality) Sodium dodecylbenzene sulfonate (LAS): sodium lauryl sulphate (SLS): 60 (SP-60) of class of department: polyoxyethylene nonylphenol ether (NP-70) is 1.0: 0.5～1.0: 0.1～0.5: 0.5～2.0 (mass ratioes), and the mass content of compound emulsifying agent in reaction system is 0.5～5%.About 0.5h of reaction times.
Second step: first stratum nucleare preparation, monomer is a butyl methacrylate, and monomer mass is 25～50% of a prepared anti-impact modifier quality, and multiple crosslinking agent is by N, N '-methylene-bisacrylamide and homemade C
4H
9OOC=CHRCH=CHCOOCH
2(R is main chain C to R '
3～C
8Alkyl, R ' is-C
3H
7) linking agent A composition, consumption is 0.1～0.6% of the first nuclear layer monomer quality, mass ratio N, N '-methylene-bisacrylamide: linking agent A=1: 0.3～1, the initiator potassium persulfate consumption is 0.3～1.5% of a monomer mass, regulation system solid content (monomer and total polymer content) 20%～40%.Later stage at the seed latex preparation feedback adds about 2h of reaction times.
The 3rd step: the preparation of second stratum nucleare, monomer adopts butyl methacrylate BA, vinylbenzene St, and monomer mass is 10～30% of a prepared anti-impact modifier quality, BA: St=1: 0.1～0.5 (quality).Multiple crosslinking agent is by Vinylstyrene and homemade C
4H
9OOC=CHRCH=CHCOOCH
2(R is main chain C to R '
3～C
8Alkyl, R ' is H) crosslinking agent B forms, consumption is 0.1～1% crosslinking agent B of amount of monomer: divinylbenzene=1: 0.1～0.4 (quality), initiator potassium persulfate consumption are 0.1～0.5% of monomer total amount; Regulation system solid content (monomer and total polymer content) 30%～50%, and add compound emulsifying agent, add-on be seed latex when preparing add-on 1/3.Later stage at the first stratum nucleare preparation feedback adds about 1h of reaction times.
The 4th step: shell preparation, adopt methyl methacrylate (MMA), vinylbenzene (St) as shell monomers, monomer mass is 10～30% of a prepared anti-impact modifier quality, MMA: St=1: 0.2～0.5 (quality), divinylbenzene is as linking agent, consumption is 0.2～2%, and initiator potassium persulfate (KPS) consumption is 0.1～0.3% of a monomer total amount, regulation system solid content 30%～50%.Later stage at the second stratum nucleare preparation feedback adds about 2h of reaction times.
The 5th step: drying, by spraying drying, control dry inlet temperature at 140 ℃～180 ℃, obtain the anti-impact modifier product, product cut size is at 150～250nm.
The invention has the beneficial effects as follows that the complete nucleocapsid structure acrylate impact that obtains according to the method described above hits properties-correcting agent and has excellent impact property, hot analyzing and testing to 3 second-order transition temperature, compare with the common nucleocapsid structure anti-impact modifier of similar composition, its shock resistance improves more than 10%.
Embodiment
Embodiment one:
The first step: the seed latex preparation, monomer is a butyl methacrylate, the massfraction that accounts for the monomer total amount is 5%, mass concentration 5%.Initiator potassium persulfate (KPS) consumption is 0.3% of a monomer mass, and linking agent is N, and N '-methylene-bisacrylamide, consumption are 0.05% of monomer mass.Compound emulsifying agent proportioning (quality) Sodium dodecylbenzene sulfonate (LAS): sodium lauryl sulphate (SLS): 60 (SP-60) of class of department: polyoxyethylene nonylphenol ether (NP-70) is 1.0: 0.5: 0.2: 1.0 (mass ratioes), mass concentration 2%.About 0.5h of reaction times.
Second step: first stratum nucleare preparation, monomer is a butyl methacrylate, and the massfraction that accounts for the monomer total amount is 40%, and linking agent is by N, N '-methylene-bisacrylamide and homemade C
4H
9OOC=CHRCH=CHCOOCH
2(R is main chain C to R '
3～C
8Alkyl, R ' is-C
3H
7) linking agent A composition, consumption is 0.3% of the first nuclear layer monomer quality, mass ratio N, N '-methylene-bisacrylamide: linking agent A=1: 0.5, the initiator potassium persulfate consumption is 0.5% of a monomer mass, regulation system solid content (monomer and total polymer content) 30%.Later stage at the seed latex preparation feedback adds about 2h of reaction times.
The 3rd step: the preparation of second stratum nucleare, monomer adopts butyl methacrylate, vinylbenzene, and the massfraction that accounts for the monomer total amount is 30%, BA: St=1: 0.2 (quality).Multiple crosslinking agent (Vinylstyrene+crosslinking agent B) consumption is 0.5% of an amount of monomer, crosslinking agent B: divinylbenzene=1: 0.2 (quality), initiator potassium persulfate consumption are 0.2% of monomer total amount; Regulation system solid content (monomer and total polymer content) 35%, and add compound emulsifying agent, add-on be seed latex when preparing add-on 1/3.Later stage at the first stratum nucleare preparation feedback adds about 1h of reaction times.
The 4th step: shell preparation, adopt methyl methacrylate (MMA), vinylbenzene (St) as shell monomers, account for the massfraction 25% of monomer total amount, MMA: St=1: 0.2 (quality), divinylbenzene crosslink agent consumption is 1% of a monomer mass, initiator potassium persulfate (KPS) consumption is 0.1% of a monomer total amount, regulation system solid content 40%.Later stage at the second stratum nucleare preparation feedback adds about 2h of reaction times.
The 5th step: drying, by spraying drying, control dry inlet temperature at ~ 160 ℃, obtain the anti-impact modifier product.
Embodiment two:
The first step: the seed latex preparation, the massfraction that the monomer butyl methacrylate accounts for the monomer total amount is 10%.
Second step: the preparation of first stratum nucleare, the monomer butyl methacrylate, the massfraction that accounts for the monomer total amount is 50%.
The 3rd step: the preparation of second stratum nucleare, the massfraction that monomer (butyl methacrylate+vinylbenzene) accounts for the monomer total amount is 20%.
The 4th step: the shell preparation, monomer (methyl methacrylate+vinylbenzene) accounts for the massfraction 20% of monomer total amount
Other is with embodiment one.
Embodiment three:
The first step: the seed latex preparation, monomer is an ethyl propenoate, the massfraction that accounts for the monomer total amount is 10%, mass concentration 10%, initiator potassium persulfate (KPS) consumption is 0.5% of a monomer mass.
Second step: the preparation of first stratum nucleare, monomer is a butyl methacrylate, the massfraction that accounts for the monomer total amount is 50%.
The 3rd step: the preparation of second stratum nucleare, the massfraction that monomer (butyl methacrylate+vinylbenzene) accounts for the monomer total amount is 20%.
The 4th step: the shell preparation, monomer (methyl methacrylate+vinylbenzene) accounts for the massfraction 20% of monomer total amount.
Other is with embodiment one.
Comparative example:
The first step: the seed latex preparation, the massfraction that the monomer butyl methacrylate accounts for the monomer total amount is 15%, mass concentration 10%, initiator potassium persulfate (KPS) consumption is 0.3% of a monomer mass, linking agent is N, and N '-methylene-bisacrylamide, consumption are 0.05% of monomer mass.Compound emulsifying agent proportioning (quality) Sodium dodecylbenzene sulfonate (LAS): sodium lauryl sulphate (SLS): 60 (SP-60) of class of department: polyoxyethylene nonylphenol ether (NP-70) is 1.0: 0.5: 0.2: 1.0 (mass ratioes), mass concentration 2%, about 0.5h of reaction times.
Second step: stratum nucleare preparation, monomer (butyl methacrylate+vinylbenzene), the massfraction that accounts for the monomer total amount is 60%, butyl methacrylate+vinylbenzene=1: 0.2 (quality), linking agent (Vinylstyrene+N, N '-methylene-bisacrylamide) consumption is 0.3% of an amount of monomer, N, N '-methylene-bisacrylamide: divinylbenzene=1: 0.2 (quality), initiator potassium persulfate consumption are 0.3% of amount of monomer.Regulation system solid content (monomer and total polymer content) 35%, and add compound emulsifying agent, add-on be seed latex when preparing add-on 1/3.Later stage at the seed latex preparation feedback adds about 1.5h of reaction times.
The 3rd step: shell preparation, monomers methyl methacrylate (MMA), vinylbenzene (St) account for the massfraction 25% of monomer total amount, MMA: St=1: 0.2 (quality), divinylbenzene crosslink agent consumption is 1% of a monomer mass, initiator potassium persulfate (KPS) consumption is 0.1% of a monomer total amount, regulation system solid content 40%.Later stage at the stratum nucleare preparation feedback adds about 2h of reaction times.
The 4th step: drying, by spraying drying, control dry inlet temperature at ~ 160 ℃, obtain the anti-impact modifier product.The invention process effect and application performance effect
The complex compounding (prescription sees Table 1) that the foregoing description and comparative example product is used for PVC, sample preparation condition: 170～175 ℃ of temperature, thin-pass 12 times, the about 0.9mm of slice thickness distinguishes sheet material on request in hydropress, at 180 ℃ of following preheating 12min, be forced into 15MPa, keep 4min, under 10MPa, be chilled to room temperature after slice, carry out following performance test respectively:
The shock strength test: be cut into the test with notched test piece batten by the GB/T1043-93 standard with omnipotent sampling machine, place after 24 hours, the strutbeam shock-testing machine carries out impact test (probe temperature: 23 ℃) between employing.
Erichsen test: be cut into the dumbbell shaped tensile bars by the GB/T1040-92 standard, use electronics universal tensile testing machine test bars tensile strength down at 23 ℃, draw speed is 20mm/min.
Vicat softening point test: test by the GB1633-79 standard-required.
Test result is as shown in table 2.
Table 1 the invention process effect test recipe
Table 2 the invention process effect
Claims (5)
1. preparation with multinuclear layer anti-impact modifier of complete nucleocapsid structure is characterized in that the preparation of this properties-correcting agent has the following steps:
(1) with butyl methacrylate or ethyl propenoate as monomer, N, N '-methylene-bisacrylamide is as linking agent, Potassium Persulphate (KPS) is as initiator, adopt Sodium dodecylbenzene sulfonate (LAS)/sodium lauryl sulphate (SLS)/class of department 60 (SP-60)/polyoxyethylene nonylphenol ether (NP-70) compound emulsifying agents, the preparation seed latex;
(2) on the seed latex basis, by the stratum nucleare that two step nucleation prepared have low glass bricking temperature, the preparation of first stratum nucleare is monomer with the butyl methacrylate, N, and N '-methylene-bisacrylamide and homemade molecular formula are C
4H
9OOC=CHRCH=CHCOOCH
2R ' wherein R is main chain C
3～C
8Alkyl R ' be-C
3H
7Bifunctional compound form multiple crosslinking agent, Potassium Persulphate (KPS) is as initiator;
(3) in the later stage of the first stratum nucleare preparation feedback, prepare second stratum nucleare by graft copolymerization, the preparation of second stratum nucleare is a monomer with butyl methacrylate, vinylbenzene, homemade molecular formula is C
4H
9OOC=CHRCH=CHCOOCH
2R ' wherein R is main chain C
3～C
8Alkyl R ' be-bifunctional compound of H and Vinylstyrene form multiple crosslinking agent, Potassium Persulphate (KPS) is as initiator;
(4) in the later stage of second stratum nucleare preparation, prepare shell by graft copolymerization with high glass-transition temperature, shell is a monomer with methyl methacrylate, vinylbenzene, homemade molecular formula is C
4H
9OOC=CHRCH=CHCOOCH
2R ' wherein R is main chain C
3～C
8Alkyl R ' be-bifunctional compound of H and Vinylstyrene form multiple crosslinking agent, Potassium Persulphate (KPS) is as initiator;
(5) react completely after, the spray-dried multinuclear layer anti-impact modifier that obtains having complete nucleocapsid structure.
2. the preparation with multinuclear layer anti-impact modifier of complete nucleocapsid structure according to claim 1, it is characterized in that: the monomer that the seed latex preparation is adopted in the above-mentioned steps (1) is a kind of in butyl methacrylate or the ethyl propenoate, monomer mass is 5～15% of a prepared anti-impact modifier quality, and the mass content of monomer in reaction system is 2～10%; Initiator potassium persulfate (KPS) consumption is 0.1～0.8% of a monomer mass, and linking agent is N, and N '-methylene-bisacrylamide, consumption are 0.01～0.1% of monomer mass; The proportioning of compound emulsifying agent is Sodium dodecylbenzene sulfonate (LAS): sodium lauryl sulphate (SLS): 60 (SP-60) of class of department: the mass ratio of polyoxyethylene nonylphenol ether (NP-70) is 1.0: 0.5～1.0: 0.1～0.5: 0.5～2.0, and the mass content of compound emulsifying agent in reaction system is 0.5～5%.
3. the preparation with multinuclear layer anti-impact modifier of complete nucleocapsid structure according to claim 1, it is characterized in that: first nuclear layer monomer is a butyl methacrylate in the above-mentioned steps (2), monomer mass is 25～50% of a prepared anti-impact modifier quality, multiple crosslinking agent is by N, N '-methylene-bisacrylamide and homemade C
4H
9OOC=CHRCH=CHCOOCH
2R ' wherein R is main chain C
3～C
8Alkyl R ' be-C
3H
7Linking agent A forms, consumption is 0.1～0.6% of the first nuclear layer monomer quality, N, and N '-methylene-bisacrylamide: the mass ratio of linking agent A is 1: 0.3～1, the initiator potassium persulfate consumption is 0.3～1.5% of a monomer mass, regulation system solid content 20%～40%.
4. the preparation with multinuclear layer anti-impact modifier of complete nucleocapsid structure according to claim 1, it is characterized in that: second nuclear layer monomer adopts butyl methacrylate (BA), vinylbenzene (St) in the above-mentioned steps (3), monomer mass is 10～30% of a prepared anti-impact modifier quality, butyl methacrylate (BA): the mass ratio of vinylbenzene (St) is 1: 0.1～0.5; Multiple crosslinking agent is by Vinylstyrene and homemade C
4H
9OOC=CHRCH=CHCOOCH
2R ' wherein R is main chain C
3～C
8Alkyl R ' be that the crosslinking agent B of H is formed, consumption is 0.1～1% of an amount of monomer, crosslinking agent B: the mass ratio of divinylbenzene is 1: 0.1～0.4, the initiator potassium persulfate consumption is 0.1～0.5% of a monomer total amount; Regulation system solid content 30%～50%.
5. the preparation with multinuclear layer anti-impact modifier of complete nucleocapsid structure according to claim 1, it is characterized in that: adopt methyl methacrylate (MMA), vinylbenzene (St) in the above-mentioned steps (4) as shell monomers, monomer mass is 10～30% of a prepared anti-impact modifier quality, methyl methacrylate (MMA): the mass ratio of vinylbenzene (St) is 1: 0.2～0.5, divinylbenzene is as linking agent, consumption is 0.2～2%, the initiator potassium persulfate consumption is 0.1～0.3% of a monomer total amount, regulation system solid content 30%～50%.
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|---|---|---|---|
| CNA2007100311000A CN101177469A (en) | 2007-10-26 | 2007-10-26 | Preparation of polynuclear layer impulse modifier having whole core-shell structure |
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|---|---|---|---|
| CNA2007100311000A CN101177469A (en) | 2007-10-26 | 2007-10-26 | Preparation of polynuclear layer impulse modifier having whole core-shell structure |
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| CN101177469A true CN101177469A (en) | 2008-05-14 |
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| CN105086263A (en) * | 2015-08-26 | 2015-11-25 | 安徽北马科技有限公司 | Composite toughening modifier for polyvinyl chloride |
| CN105683229A (en) * | 2013-07-02 | 2016-06-15 | 陶氏环球技术有限责任公司 | Polyolefin/ (meth)acrylic impact modifier and method of preparing same |
| CN105860351A (en) * | 2016-04-28 | 2016-08-17 | 安徽扬天塑业科技有限公司 | 70-DEG C protective-layer-level soft polyvinyl chloride butyronitrile material |
| CN105906974A (en) * | 2016-04-28 | 2016-08-31 | 安徽扬天塑业科技有限公司 | 70 degrees centigrade sheath grade flexible elastic polyvinyl chloride material |
| CN111205399A (en) * | 2020-03-03 | 2020-05-29 | 长春工业大学 | Method for improving grafting efficiency of PBA-g-MMA graft copolymer |
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| CN105086263A (en) * | 2015-08-26 | 2015-11-25 | 安徽北马科技有限公司 | Composite toughening modifier for polyvinyl chloride |
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| CN105906974A (en) * | 2016-04-28 | 2016-08-31 | 安徽扬天塑业科技有限公司 | 70 degrees centigrade sheath grade flexible elastic polyvinyl chloride material |
| CN111205399A (en) * | 2020-03-03 | 2020-05-29 | 长春工业大学 | Method for improving grafting efficiency of PBA-g-MMA graft copolymer |
| CN112646495A (en) * | 2021-02-08 | 2021-04-13 | 华南理工大学 | Lignin/polyether polyol impact-resistant self-healing coating and preparation method thereof |
| CN112646495B (en) * | 2021-02-08 | 2022-06-14 | 华南理工大学 | Lignin/polyether polyol impact-resistant self-healing coating and preparation method thereof |
| CN113004469A (en) * | 2021-03-05 | 2021-06-22 | 威海金合思化工有限公司 | PVC product toughening agent for low-temperature environment and preparation method thereof |
| CN113004453A (en) * | 2021-03-08 | 2021-06-22 | 威海金合思化工有限公司 | Optical-grade transparent PMMA toughening agent and preparation method thereof |
| CN113402675A (en) * | 2021-08-23 | 2021-09-17 | 山东昌泰高分子材料股份有限公司 | Preparation method of acrylate impact modifier |
| CN113402675B (en) * | 2021-08-23 | 2021-11-09 | 山东昌泰高分子材料股份有限公司 | Preparation method of acrylate impact modifier |
| CN115232262A (en) * | 2022-03-09 | 2022-10-25 | 威海金合思化工有限公司 | Acrylate impact modifier for transparent PVC (polyvinyl chloride) products and preparation method thereof |
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