CN1412232A - Preparation method of novel impact modifier acrylate resin (ACR-II) of polyvinyl chloride (PVC) - Google Patents
Preparation method of novel impact modifier acrylate resin (ACR-II) of polyvinyl chloride (PVC) Download PDFInfo
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- CN1412232A CN1412232A CN 01136255 CN01136255A CN1412232A CN 1412232 A CN1412232 A CN 1412232A CN 01136255 CN01136255 CN 01136255 CN 01136255 A CN01136255 A CN 01136255A CN 1412232 A CN1412232 A CN 1412232A
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- acr
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- pvc
- polyvinyl chloride
- acrylic resin
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- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 31
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000004609 Impact Modifier Substances 0.000 title abstract description 7
- 239000000839 emulsion Substances 0.000 claims abstract description 37
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 21
- -1 methacrylic acid glycol ester Chemical class 0.000 claims description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 7
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 6
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 5
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 5
- 230000007704 transition Effects 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 239000004159 Potassium persulphate Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims 1
- 239000004141 Sodium laurylsulphate Substances 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims 1
- 239000003995 emulsifying agent Substances 0.000 claims 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 238000001694 spray drying Methods 0.000 abstract description 4
- 229920003023 plastic Polymers 0.000 abstract description 3
- 239000004033 plastic Substances 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000004709 Chlorinated polyethylene Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- SRBFZHDQGSBBOR-LECHCGJUSA-N alpha-D-xylose Chemical compound O[C@@H]1CO[C@H](O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-LECHCGJUSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000000796 flavoring agent Substances 0.000 description 4
- 235000019634 flavors Nutrition 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 235000012976 tarts Nutrition 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 229960003487 xylose Drugs 0.000 description 4
- 238000000926 separation method Methods 0.000 description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- Graft Or Block Polymers (AREA)
Abstract
The invention relates to a preparation method of acrylic resin (ACR-II) used as a novel impact modifier for polyvinyl chloride (PVC), which adopts a core/shell combined grafting agent, a rubber-plastic compatilizer and a composite inorganic salt modified seed emulsion to realize a spray drying technology.
Description
2. affiliated technical field:
Anti-impact modifier ACR-II is the toughner of polyvinyl chloride (PVC) profiled material.The traditional method for toughening of profile extrustion die of polyvinyl chloride mainly adopts and adds chlorinatedpolyethylene (CPE).Because after the CPE modified PVC, the shock strength of PVC profiled material, tensile strength, modulus, heat-drawn wire and weathering resistance are far away from ACR modified PVC profiled material.The proportioning of adding during with ACR-II is less, and when adding 5～6phr, the shock strength of PVC profiled material is higher than the performance of adding 8～10phr CPE, and the processing temperature scope is wideer than CPE.The PVC profiled material weathering resistance of particularly adding ACR is better than adding CPE greatly.In a word, ACR modified PVC profiled material is celebrated with its excellent combination property.
3. technical background:
Before the present invention, U.S. Rohm and Haas company once delivered anti-impact modifier ACR-II technology of preparing patent, and the patent No. is US5, and 312,575, the day for announcing is 19940517.This patent has been introduced the technology of preparing of core/shell structure anti-impact modifier, prepares low particle size emulsion by the letex polymerization the first step; Second step was carried out microcoacervation; The 3rd step formed microcapsule and adopted spray drying technology or condensation technique technology to realize product separation.Emulsion particle diameter d=60～the 70nm of the art of this patent preparation, less than normal, be unfavorable for the raising of anti-impact modifier ACR shock resistance, combine closely in conjunction with the chemical bond formation of having no backing between the nuclear/shell in addition.
4. Fa Ming purpose:
The objective of the invention is to overcome the shortcoming of above-mentioned patent, prepare big particle diameter ACR-II emulsion, improve the combination between the nuclear/shell, form self-patented technology.(1) increases nuclear/capsomere footpath, can reach 300nm; To improve the ACR-II impact resistance; (2) introduce grafting agent, by chemical graft between the nuclear/shell, the realization nucleocapsid is combined closely; (3) introduce the phase compatilizer, realize that nuclear/shell out-phase is compatible, raising rubber and plastic interface is compatible.5. summary of the invention:
Adopt the seeded emulsion polymerization technology, between control karyosome footpath d=70～300nm, fully improve anti-impact modifier ACR-II shock resistance.Nuclear monomer is selected second-order transition temperature T for use
g≤-20 ℃ of monomers are as butyl acrylate, ethyl propenoate, isobutyl acrylate etc.; Nuclear monomer accounts for total nuclear amount 90-100%.For the polymerization of modification seed emulsion, need to add inorganic salt, as Ca
2Cl, NaCl, HCl, Na
2CO
3, NaHCO
3, NH
3H
2O, the PH=6.5 of emulsion system～7.5.Adopt second-order transition temperature T
g〉=80 ℃ shell monomer, shell polymerization temperature are controlled at 70～90 ℃, and nuclear/shell ratio of components is 80～50: 20～50.Compound that employing contains the two keys of a plurality of different bond energys is as 1,4-butyleneglycol double methacrylate, methacrylic acid glycol ester, and 1,6-hexylene glycol double methacrylate etc. participates in polyreaction as grafting agent, grafting agent accounts for nuclear total amount 0-5%.Active high two keys have at first participated in the nuclear polyreaction, and active low two keys have a part and have neither part nor lot in polyreaction, when waiting until the formation shell, play graft reaction as the MMA of active site and shell, and nuclear/shell is combined closely; Also there is the compatible problem in interface in the stratum nucleare rubber phase mutually with the shell plastics, in the hud polymerization process, adds the molecular weight M that accounts for nuclear total amount 0-5%
W=2000～5000 polymethylmethacrylate (PMMA) helps between the compatible realization nucleocapsid in interface Chemical bond being arranged not only, and also has physical compatibility, finishes perfect adaptation between nuclear/shell.The nuclear polymerization temperature is controlled at 70～90 ℃.6. invention effect:
Adopt the seeded emulsion polymerization technology, between control karyosome footpath d=70～300nm, than patent US5,312,575 karyosomes footpath d=60～70nm enlarges markedly; Introduce grafting agent and compatilizer mutually, both realized chemical graft between nuclear/shell, realized the physical compatibility of nuclear/shell out-phase again, than microcoacervation, microcapsule shell/nuclear coats, and the combination of nuclear/shell is tight.
7. embodiment: (1) embodiment 1
Butyl polyacrylate (PBA) is 70: 30 (wt) with the ratio of polymethylmethacrylate (PMMA).
Adopt the Multi-stage seed emulsion polymerization method, realize the control of karyosome footpath size.Be dissolved in the 179.32g butyl acrylate (BA) 1.944g1,4-butyleneglycol double methacrylate standby.In the 1000ml reactor, add 600g deionized water, 2.2g sodium laurylsulfonate (SLS), 1.0gNaOH, 0.8g Potassium Persulphate (kps) and 80.64gBA mixed solution, under 75 ℃ of conditions, react 30min, drip remaining BA mixed solution then, 1.0hr in drip off, the reaction 30min.The seed emulsion preparation finishes.
Adding 0.3g isopropyl benzene hydroperoxide, 1.56g1,4-butyleneglycol double methacrylate, 1.05g toxilic acid allyl ester, 0.26g wood sugar and 1.2gSLS, 19.85gPMMA and 100g water mix and make pre-emulsion in 179.32gBA.
In the 1000ml reactor, add 400g water, 1.86gSLS and 19.65g seed emulsion and 0.21g trimeric cyanamide.Under 75 ℃, drip above-mentioned pre-emulsion, 1.5hr dropwises, reaction 1.0hr.Reaction system is carried out under nitrogen protection, and oxygen level is no more than 60ppm.The preparation of butyl polyacrylate (PBA) nuclear particle is finished.
The PBA seed emulsion is warming up to 85 ℃, drips 21.86g methyl methacrylate (MMA) and 0.06g isopropyl benzene hydroperoxide, 0.5hr adds, reaction 0.5hr.The acrylic ester emulsion that reaction finishes is warming up to 90 ℃, adds 10%HCL30g, 10%NaHCO
325g stirs 30min.
Acrylic ester emulsion is cooled to 85 ℃, and 43.73gMMA drips 1.0hr, drips the 0.03g lauryl mercaptan simultaneously, 0.12g isopropyl benzene hydroperoxide, 0.12g trimeric cyanamide and 0.16g wood sugar, reaction 1.0hr.Adopt spray drying technology can realize product separation.Table 1 seed emulsion and PBA karyosome directly concern numbering seed emulsion amount, the ml size, and d/nm1 400
a702 200 903 100 1,204 50 1,605 20 2,006 10 260a all adopt seed emulsion to examine
PBA karyosome footpath increases with the minimizing of seed emulsion consumption as seen from Table 1.Both meet following relation substantially: (D/d)
3=n/N, the karyosome footpath when D is whole seed emulsion direct polymerization in the formula; D carries out seeded emulsion polymerization gained karyosome footpath during for n for the seed consumption; N is the seed emulsion total amount; N is the seed emulsion consumption when carrying out seeded emulsion polymerization.This presentation of results adopts seeded emulsion polymerization may command PBA karyosome footpath size.Table 2 oxygen to polyreaction to influence the normal 60 0.4 90 emulsion tart flavours of normal 50 0.36 99.6 reactions of normal 40 0.35 99.8 reactions of oxygen level oxygen level transformation efficiency % gas phase ppm liquid phase mg/l20 0.3 99.9 reaction as a result big, sticking
Wall 70 0.42 85 emulsion tart flavours are big, and are sticking
Wall (2) embodiment 2
Butyl polyacrylate (PBA) is 80: 20 (wt) with the ratio of polymethylmethacrylate (PMMA).
Adopt the Multi-stage seed emulsion polymerization method, realize the control of karyosome footpath size.Be dissolved in the 179.32g butyl acrylate (BA) 1.944g1,4-butyleneglycol double methacrylate standby.In the 1000ml reactor, add 600g deionized water, 2.2g sodium laurylsulfonate (SLS), 1.0gNaOH, 0.8g Potassium Persulphate (kps) and 80.64gBA mixed solution, under 75 ℃ of conditions, react 30min, drip remaining BA mixed solution then, 1.0hr in drip off, the reaction 30min.The seed emulsion preparation finishes.
Add 0.3g isopropyl benzene hydroperoxide, 1.56g1,4-butyleneglycol double methacrylate in 179.32gBA, 1.05g toxilic acid allyl ester, 0.27g wood sugar and 1.2gSLS, 10.01gPMMA and 100g water mix makes pre-emulsion.
In the 1000ml reactor, add 400g water, 1.84gSLS and 19.65g seed emulsion and 0.23g trimeric cyanamide.Under 75 ℃, drip above-mentioned pre-emulsion, 1.5hr dropwises, reaction 1.0hr.Reaction system is carried out under nitrogen protection, and oxygen level is no more than 60ppm.The preparation of butyl polyacrylate (PBA) nuclear particle is finished.
The PBA seed emulsion is warming up to 85 ℃, drips 21.85g methyl methacrylate (MMA) and 0.06g isopropyl benzene hydroperoxide, 0.5hr adds, reaction 0.5hr.The acrylic ester emulsion that reaction finishes is warming up to 90 ℃, adds 10%HCL30g, 10%NaHCO
325g stirs 30min.
Acrylic ester emulsion is cooled to 85 ℃, and 18gMMA drips 0.5hr, drips the 0.02g lauryl mercaptan simultaneously, 0.08g isopropyl benzene hydroperoxide, 0.09g trimeric cyanamide and 0.14g wood sugar, reaction 1.0hr.Adopt spray drying technology can realize product separation.Table 3 seed emulsion and PBA karyosome directly concern numbering seed emulsion amount, the ml size, and d/nm1 400
a702 200 903 100 1,204 50 1,655 20 2,106 10 270a all adopt seed emulsion do nuclear table 4 oxygen to polymerisation to affect the normal 60 0.42 89.5 emulsion tart flavours of normal 50 0.40 99.7 reactions of normal 40 0.38 99.8 reactions of as a result gas phase ppm liquid phase mg/l20 0.32 99.8 reaction of oxygen content oxygen content conversion ratio % big, sticking
Wall 70 0.42 82 emulsion tart flavours are big, and are sticking
Wall
Claims (8)
1, the preparation method of polyvinyl chloride (PVC) novel anti impact modifying agent acrylic resin (ACR-II) is characterized in that adopting the method for Multi-stage seed emulsion polymerization, adopts second-order transition temperature T
g≤ 20 ℃ nuclear monomer adds grafting agent, adds deionized water, emulsifying agent, water-soluble and/or oil-soluble initiator then, reacts under 70～90 ℃ of temperature, makes seed emulsion, adds linking agent again and makes pre-emulsion, adopts second-order transition temperature T
g〉=80 ℃ shell monomer, shell polymerization temperature are controlled at 70～90 ℃, and nuclear/shell ratio of components is 80～50: 20～50; Employing contains a plurality of double bond compounds and participates in polyreaction as grafting agent, and grafting agent adds the molecular weight M that accounts for nuclear total amount 0-5%
W=2000～5000 polymethylmethacrylate (PMMA) is as phase solvent, and the nuclear polymerization temperature is controlled at 70～90 ℃.
2, according to the preparation method of the described polyvinyl chloride of claim 1 (PVC) novel anti impact modifying agent acrylic resin (ACR-II), it is characterized in that second-order transition temperature T
g≤ 20 ℃ nuclear monomer adopts butyl acrylate, ethyl propenoate, isobutyl acrylate.
3, according to the preparation method of the described polyvinyl chloride of claim 1 (PVC) novel anti impact modifying agent acrylic resin (ACR-II), it is characterized in that T
g〉=80 ℃ shell monomer is to adopt vinylbenzene, methyl methacrylate.
4,, it is characterized in that adopting 1,4 butyleneglycol double methacrylates, methacrylic acid glycol ester, 1,6-hexylene glycol double methacrylate, toxilic acid allyl ester according to the preparation method of the described polyvinyl chloride of claim 1 (PVC) novel anti impact modifying agent acrylic resin (ACR-II).
5, according to the preparation method of the described polyvinyl chloride of claim 1 (PVC) novel anti impact modifying agent acrylic resin (ACR-II), it is characterized in that sodium laurylsulfonate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate.
6,, it is characterized in that the oil-soluble initiator that is adopted among acrylic resin (ACR-II) preparation method adopts Potassium Persulphate according to the preparation method of the described polyvinyl chloride of claim 1 (PVC) novel anti impact modifying agent acrylic resin (ACR-II).
7,, it is characterized in that the complex inorganic salt catalyst of modification seed emulsion comprises CaCl according to the preparation method of the described polyvinyl chloride of claim 1 (PVC) novel anti impact modifying agent acrylic resin (ACR-II)
2, NaCl, HCL, Na
2CO
3, NaHCO
3, NH
3H
2O.
8,, it is characterized in that the oil-soluble initiator that is adopted among acrylic resin (ACR-II) preparation method can adopt isopropyl benzene hydroperoxide and trimeric cyanamide according to the preparation method of the described polyvinyl chloride of claim 1 (PVC) novel anti impact modifying agent acrylic resin (ACR-II).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01136255 CN1412232A (en) | 2001-10-12 | 2001-10-12 | Preparation method of novel impact modifier acrylate resin (ACR-II) of polyvinyl chloride (PVC) |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01136255 CN1412232A (en) | 2001-10-12 | 2001-10-12 | Preparation method of novel impact modifier acrylate resin (ACR-II) of polyvinyl chloride (PVC) |
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| CN1412232A true CN1412232A (en) | 2003-04-23 |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348657C (en) * | 2003-07-24 | 2007-11-14 | 赵东日 | Polyvingyl chloride mixture with weather resistance, shock resistance and excellent workability |
| CN100398574C (en) * | 2005-08-19 | 2008-07-02 | 沂源瑞丰高分子材料有限公司 | Separating agent in acr in use for impact modifier, and method of use |
| CN100547027C (en) * | 2006-11-18 | 2009-10-07 | 沂源瑞丰高分子材料有限公司 | PVC ultra-large particle diameter high-fluidity acrylic ester impact modifier |
| CN101870751A (en) * | 2010-07-08 | 2010-10-27 | 河北工业大学 | A kind of preparation method of nylon 6 toughening acrylate functionalized copolymer |
| CN101434678B (en) * | 2007-11-16 | 2011-01-12 | 山东瑞丰高分子材料股份有限公司 | Hard PVC resin additive for special-shaped section bar |
| CN101328241B (en) * | 2007-06-18 | 2011-07-20 | 山东瑞丰高分子材料股份有限公司 | Processing modifying agent for polychloroethylene foaming moulding products |
| CN102225979A (en) * | 2011-04-28 | 2011-10-26 | 内江市运通塑料助剂有限公司 | Preparation method and product of vinyl chloride, acrylate multi-copolymerized resin by mass polymerization process |
| CN103073670A (en) * | 2012-12-24 | 2013-05-01 | 席文峰 | Impact modifier ACR resin and preparation method thereof |
| CN103467664A (en) * | 2013-09-13 | 2013-12-25 | 四川凯本新材料科技有限公司 | Preparation method of flame-retardant, impact-resistant and high-fluidity chloroethylene-based special resin |
| CN101421344B (en) * | 2006-02-14 | 2014-12-17 | 阿克马法国公司 | Hybrid impact modifiers and method for preparing the same |
| CN104327210A (en) * | 2013-07-22 | 2015-02-04 | 南通艾德旺化工有限公司 | Preparation of high-viscosity foaming-type modifier ACR (acrylate resin) |
| CN108948263A (en) * | 2018-07-05 | 2018-12-07 | 江西岳峰集团高分子材料有限公司 | A kind of modifier A CR of resistant to thermal aging |
-
2001
- 2001-10-12 CN CN 01136255 patent/CN1412232A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348657C (en) * | 2003-07-24 | 2007-11-14 | 赵东日 | Polyvingyl chloride mixture with weather resistance, shock resistance and excellent workability |
| CN100398574C (en) * | 2005-08-19 | 2008-07-02 | 沂源瑞丰高分子材料有限公司 | Separating agent in acr in use for impact modifier, and method of use |
| CN101421344B (en) * | 2006-02-14 | 2014-12-17 | 阿克马法国公司 | Hybrid impact modifiers and method for preparing the same |
| CN100547027C (en) * | 2006-11-18 | 2009-10-07 | 沂源瑞丰高分子材料有限公司 | PVC ultra-large particle diameter high-fluidity acrylic ester impact modifier |
| CN101328241B (en) * | 2007-06-18 | 2011-07-20 | 山东瑞丰高分子材料股份有限公司 | Processing modifying agent for polychloroethylene foaming moulding products |
| CN101434678B (en) * | 2007-11-16 | 2011-01-12 | 山东瑞丰高分子材料股份有限公司 | Hard PVC resin additive for special-shaped section bar |
| CN101870751A (en) * | 2010-07-08 | 2010-10-27 | 河北工业大学 | A kind of preparation method of nylon 6 toughening acrylate functionalized copolymer |
| CN101870751B (en) * | 2010-07-08 | 2012-05-02 | 河北工业大学 | A kind of preparation method of nylon 6 toughening acrylate functionalized copolymer |
| CN102225979A (en) * | 2011-04-28 | 2011-10-26 | 内江市运通塑料助剂有限公司 | Preparation method and product of vinyl chloride, acrylate multi-copolymerized resin by mass polymerization process |
| CN103073670A (en) * | 2012-12-24 | 2013-05-01 | 席文峰 | Impact modifier ACR resin and preparation method thereof |
| CN103073670B (en) * | 2012-12-24 | 2015-10-07 | 席文峰 | impact modifier ACR resin and preparation method thereof |
| CN104327210A (en) * | 2013-07-22 | 2015-02-04 | 南通艾德旺化工有限公司 | Preparation of high-viscosity foaming-type modifier ACR (acrylate resin) |
| CN103467664A (en) * | 2013-09-13 | 2013-12-25 | 四川凯本新材料科技有限公司 | Preparation method of flame-retardant, impact-resistant and high-fluidity chloroethylene-based special resin |
| CN108948263A (en) * | 2018-07-05 | 2018-12-07 | 江西岳峰集团高分子材料有限公司 | A kind of modifier A CR of resistant to thermal aging |
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