CN101186671A - N-substituted maleimide heat-resistance modifier containing rare earth, preparation method and application thereof - Google Patents
N-substituted maleimide heat-resistance modifier containing rare earth, preparation method and application thereof Download PDFInfo
- Publication number
- CN101186671A CN101186671A CNA2007101501888A CN200710150188A CN101186671A CN 101186671 A CN101186671 A CN 101186671A CN A2007101501888 A CNA2007101501888 A CN A2007101501888A CN 200710150188 A CN200710150188 A CN 200710150188A CN 101186671 A CN101186671 A CN 101186671A
- Authority
- CN
- China
- Prior art keywords
- heat
- pvc
- substituted maleimide
- rare earth
- toxilic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a N-substituted maleimide heat resistant modifier containing rare-earth, which is prepared by following steps as processing raw materials, adding water, emulsifier and initiator into a reactor, adding mixture monomer of N-substituted maleimide, maleate rare-earth, methyl methacrylate and phenylethene, raising temperature and reacting, demulsifying via octadecanoic hydrone aluminum sulfate solution, washing and drying, to obtain N-substituted maleimide heat resistant modifier containing rare-earth. The inventive heat resistant modifier can improve heat resistance and stability of PVX, while the soften point of the blended and modified PVC vicat is improved of 4.7DEG C than pure PVC, the initial heat decomposition temperature is improved of 6.70DEG C than pure PVC, and the temperature at 50% of heat loss is improved of 17.31DEG C than pure PVC. The blended and modified PVC has better mechanical property, which impact strength and tensile strength are respectively improved of 1.62% and 3.35% than pure PVC.
Description
Technical field
The present invention relates to have certain stable on heating multiple copolymer, particularly a kind of N-substituted maleimide heat-resistance modifier that contains rare earth and its production and application by heat resistance modified monomer and organic RE copolymerization.
Background technology
Polyvinyl chloride (PVC) is one of most widely used at present, that output is maximum general-purpose plastics, have low price, good, the difficult combustion of the transparency, electrical insulating property is good and advantage such as chemicals-resistant, can be by adding various additives and using multiple forming method make different, the broad-spectrum soft or rigid plastics goods of performance.But the poor heat resistance of PVC boardy product, its heat-drawn wire are 78～80 ℃, and continuously use temperature only about 65 ℃, and PVC is easily decomposed in the course of processing, and these make the range of application of PVC be subjected to very big restriction.
N-substituted maleimide amine has the raising thermotolerance, and advantage such as, Heat stability is good good, nontoxic with various resin compatibles has become a heat resistance modified important channel of macromolecular material since the eighties in 20th century.Multiple N-substituted maleimide amine can with the vinyl monomer copolymerization, obviously improve corresponding copolymers thermal characteristics or as heat-proof modifier improve other general-purpose plastics thermal characteristics (see synthetic resins and plastics, 2004,21 (3), Wu Weihong etc.; Zhejiang University's master thesis, 2006,2, of exceptional ability recklessly).N-cyclohexyl maleimide is a kind of preferably in the N-substituted maleimide amine, copolymer-modified PVC with N-cyclohexyl maleimide and vinyl monomer has good thermal characteristics, but when the PVC thermal characteristics improves, because the adding of rigid radical, often cause its mechanical properties decrease (to see Chinese plastics, 2003,17 (5), Yang Liting etc.).
Rare earth thermal stabilizer is the new stabilizer system that development in recent years is got up, and it has characteristics efficient, nontoxic, that synergetic property is good, has obtained using widely in PVC.With fastest developing speed in state's internal stabilizer with nontoxic rare earth class stablizer, and the toxilic acid monoester rare earth has special structure, two keys in its structure can carry out copolymerization with vinyl monomer, ester chain in the structure can increase the kindliness of polymkeric substance, the chlorine atom of rare earth ion on it on can complexing PVC chain improves the thermostability of PVC.Yet at present for the research of toxilic acid monoester rare earth, also only be with its as the one-component blending in polyvinyl chloride, play certain thermostability (see Chinese plastics, 2002,16 (1), Liu Jianping etc.; Modern plastics processed and applied, 2001,13 (1), Wu Maoying etc.), and low molecule organic RE thermo-stabilizer is easy to migration, influences the performance of PVC.
We have introduced the toxilic acid monoester rare earth that has flexible ester group in traditional N-substituted maleimide amine-vinylbenzene-methyl methacrylate heat-proof modifier system for these reasons, with this tetrapolymer and PVC blend, in the hope of obtaining the good polyvinyl chloride resin of thermotolerance height, Heat stability is good, mechanical property and processing characteristics, to widen the Application Areas of PVC.
Summary of the invention
The objective of the invention is at the problems referred to above, provide a kind of by the toxilic acid monoester rare earth as the thermally-stabilised composition of PVC, N-substituted maleimide amine properties-correcting agent as heat resistance modified monomer and methyl methacrylate, styrene copolymerisation, this properties-correcting agent can keep under the constant or prerequisite that improves of mechanical property PV ℃ of heat-proof modifier of preparation high-performance.
Technical scheme of the present invention:
A kind of N-substituted maleimide heat-resistance modifier that contains rare earth is characterized by as follows and makes:
The composition quality umber
Monomer:
N-substituted maleimide amine (RMI) 10
Toxilic acid monoester rare earth 5～25
Methyl methacrylate (MMA) 10～70
Vinylbenzene (St) 10～60
Initiator:
2～4 ‰ of Potassium Persulphate monomer total amount
Emulsifying agent:
2～6% of sodium lauryl sulphate (SDS) monomer total amount
200～800% of deionized water monomer total amount
N-substituted maleimide amine recited above is specially: N-cyclohexyl maleimide or N-phenylmaleimide;
(1) raw material is handled: methyl methacrylate and vinylbenzene are all removed stopper through the underpressure distillation purifying in the above used monomer;
(2) preparation of heat-proof modifier: by top proportioning, agitator is being housed, thermometer, in the reactor of reflux condensing tube, add entry, emulsifying agent, feed nitrogen simultaneously, heating in water bath to 75 ℃, add initiator, begin dropping by constant pressure funnel and consist of N-substituted maleimide amine, the toxilic acid monoester rare earth, methyl methacrylate and cinnamic mix monomer, dripped monomer in 1-2 hour, continue heating and make system be warmed up to 80 ℃, reaction 1-2 hour is warmed up to 85 ℃ again, reaction 0.5-1 hour, use 18 water alum liquor breakdown of emulsion then, washing, oven dry, obtain the white powder solid, promptly contain the N-substituted maleimide heat-resistance modifier of rare earth.
Toxilic acid monoester rare earth recited above is specially: toxilic acid list ten diester lanthanums, toxilic acid list ten diester ceriums or toxilic acid list ten diester neodymiums.
Above the described application that contains the N-substituted maleimide heat-resistance modifier of rare earth, it is characterized by this N-substituted maleimide heat-resistance modifier as the thermo-stabilizer that improves the PVC thermostability, preparation process is as follows:
The proportioning of blending and modifying PVC:
The composition quality umber
PVC 100
Top gained heat-proof modifier 10-40
Jing Xi-8,831 2.5
Calcium stearate 0.8
Stearyl alcohol 0.8
According to said ratio, with mixing on two roll plastic mixing mill after each component high-speed mixing of blending and modifying PVC, two roll temperatures obtain flaky material between 160-180 ℃, then between 170-200 ℃, being pressed into smooth sheet material on the plastic product hydraulic press, at last by omnipotent sampling machine sample preparation.
Produce the test bars of Vicat softening point tests by GB1633-79; Producing the charpy impact test batten by GB1043-93 tests; Producing the Erichsen test batten by GB1040-92 tests.
The heat-proof modifier that the inventive method obtains both can improve the thermotolerance of PVC to a certain extent, can improve the thermostability of PVC again simultaneously, and the blending and modifying PVC good mechanical properties that obtains.
Beneficial effect of the present invention is:
The N-substituted maleimide heat-resistance modifier that contains rare earth that the present invention is prepared has higher thermotolerance.Compared to the prior art, added the toxilic acid monoester rare earth among the present invention as functional monomer, the flexible ester group in this monomer can improve the mechanical property of blend PVC, and rare earth ion can improve the thermostability of PVC.Therefore the heat-proof modifier of the present invention's preparation has not only improved the use temperature of PVC, and has improved the thermostability of PVC, and mechanical property also obtains raising in various degree, and especially the shock strength of PVC does not only descend, and increases on the contrary.The consumption of toxilic acid list ten diester lanthanums is 5.5 parts in polymkeric substance, when N-cyclohexyl maleimide consumption is 10 parts, use this heat-proof modifier and 100 parts of PVC blend of 20 parts, the Vicat softening point of gained blending and modifying PVC has improved 4.7 ℃ than pure PVC, initial heat decomposition temperature (temperature during thermal weight loss 10%) has improved 6.70 ℃ than pure PVC, temperature during thermal weight loss 50% is compared with pure PVC and has been improved 17.31 ℃, and shock strength, tensile strength are compared with pure PVC and improved 1.62% and 3.35% respectively.
Another advantage of the present invention is that raw material sources are convenient, and cheap, preparation technology is simple, and the blending and modifying PVC of gained compares with pure PVC and has the good transparency.The modified PVC of the present invention's preparation can be widely used in heat-resisting bottle, electric appliance casing, pipeline connection, battery frid and heat-resisting water pipe etc., is good engineering plastics surrogate.
Embodiment:
Raw material is handled: monomers methyl methacrylate and vinylbenzene used among the embodiment are all removed stopper through the underpressure distillation purifying.
Embodiment 1:
Contain the preparation of the N-substituted maleimide amine heat-proof modifier of rare earth: in the reactor that agitator, thermometer, reflux condensing tube are housed, add the 120ml deionized water, 1.5013g emulsifying agent, logical N
2, begin to stir; Adding 3.0009g toxilic acid list ten diester lanthanums, 2.7011gN-cyclohexyl maleimide, 18.9128g methyl methacrylate, 5.4012g vinylbenzene mix its dissolving in small beaker, pour in the constant pressure funnel.Add initiator when temperature rises to 75 ℃ in the question response device: Potassium Persulphate 0.0892g, begin to drip monomer, keep 75 ℃ and N
2Atmosphere drips off to monomer, makes system be warming up to 80 ℃ of reactions 1 hour then, is warming up to 85 ℃ of reactions 0.5 hour again, and is complete with the bonding precursor reactant.Reaction finishes, and product is a white emulsion, with 18 water alum liquor breakdown of emulsion, obtains the white powder solid behind the deionized water wash.The second-order transition temperature of this heat-proof modifier is 124.80 ℃.
Embodiment 2-4:
Operation is with embodiment 1, and difference is the consumption difference of toxilic acid list ten diester lanthanums in the heat resistance modified agent prescription, sees Table 1.
The second-order transition temperature of the heat-proof modifier of the different toxilic acid list ten diester lanthanum consumptions of table 1
| Numbering | Toxilic acid list ten diester lanthanums (g) | Second-order transition temperature (℃) |
| Embodiment 2 embodiment 3 embodiment 4 | 1.5002 4.5019 6.0002 | 117.23 125.27 123.98 |
Embodiment: 5
Operation is with embodiment 1, and it is toxilic acid list ten diester ceriums that difference is employed, and concrete proportioning is as follows: toxilic acid list ten diester cerium 3.0015g, N-cyclohexyl maleimide 2.7008g, methyl methacrylate 18.9060g, vinylbenzene 5.4011g.The second-order transition temperature of gained heat-proof modifier is 124.23 ℃.
Embodiment: 6
Operation is with embodiment 1, and it is toxilic acid list ten diester neodymiums that difference is employed, and concrete proportioning is as follows: toxilic acid list ten diester neodymium 3.0021g, N-cyclohexyl maleimide 2.7014g, methyl methacrylate 18.9005g, vinylbenzene 5.4029g.The second-order transition temperature of gained heat-proof modifier is 123.79 ℃.
Embodiment 7:
Operation is with embodiment 1, and it is N-phenylmaleimide that difference is employed, and concrete proportioning is as follows: toxilic acid list ten diester lanthanum 3.0005g, N-phenylmaleimide 5.4006g, methyl methacrylate 10.8060g, vinylbenzene 10.8011g.The second-order transition temperature of this heat-proof modifier of gained is 137.34 ℃.
Embodiment 8:
The preparation of blending and modifying PVC: get 225.0gPVC, the heat-proof modifier of 45.0g embodiment 1 gained, 5.6g Jing Xi-8831,1.8g calcium stearate, 1.8g stearyl alcohol, after mixing on the high-speed mixer, mixing on two roll plastic mixing mill again, two roll temperatures are between 160-180 ℃, obtain flaky material, then between 170-200 ℃, being pressed into smooth sheet material on the plastic product hydraulic press, at last by omnipotent sampling machine sample preparation.
Produce the test bars of Vicat softening point tests by GB1633-79; Producing the charpy impact test batten by GB1043-93 tests; Producing the Erichsen test batten by GB1040-92 tests.The Vicat softening point of gained blending and modifying PVC is 85.4 ℃, initial heat decomposition temperature Td
10(temperature during thermal weight loss 10%): 290.80 ℃, heat decomposition temperature Td
50(temperature during thermal weight loss 50%): 335.75 ℃, shock strength: 3.46kJ/m
2, tensile strength: 59.88MPa.
Embodiment 9-11:
Operation is with embodiment 8, and difference is heat-proof modifier difference used among the blending and modifying PVC, sees Table 2.
Thermal characteristics and the mechanical property of the heat-proof modifier blending and modifying PVC of the different toxilic acid list ten diester lanthanum consumptions of table 2
| Numbering | Heat-proof modifier | Vicat softening point (℃) | Initial heat decomposition temperature (Td 10℃) | Heat decomposition temperature (Td 50℃) | Shock strength (kJ/m 2) | Tensile strength (Mpa) |
| Embodiment 9 embodiment 10 embodiment 11 | Synthetic synthetic synthetic by embodiment 2 by embodiment 4 by embodiment 3 | 87.6 84.2 84.1 | 291.63 288.70 289.82 | 338.54 334.63 335.19 | 4.39 5.36 3.95 | 60.72 58.86 58.23 |
Annotate: the Vicat softening point of pure PVC is 82.9 ℃, weightless 10% o'clock heat decomposition temperature Td
10: 284.93 ℃, weightless 50% o'clock heat decomposition temperature Td
50: 321.23 ℃, shock strength: 4.32kJ/m
2, tensile strength: 58.75MPa
Embodiment 12,13:
Operation is with embodiment 8, and difference is heat-proof modifier difference used among the blending and modifying PVC, sees Table 3.
Table 3 contains thermal characteristics and the mechanical property of the heat-proof modifier blending and modifying PVC of different toxilic acid monoester rare earths
| Numbering | Heat-proof modifier | Vicat softening point (℃) | Initial heat decomposition temperature (Td 10℃) | Heat decomposition temperature (Td 50℃) | Shock strength (kJ/m 2) | Tensile strength (Mpa) |
| Embodiment 12 embodiment 13 | Synthetic synthetic by embodiment 5 by embodiment 6 | 85.2 84.9 | 290.03 289.56 | 334.64 333.23 | 3.37 3.05 | 59.23 58.76 |
Annotate: the Vicat softening point of pure PVC is 82.9 ℃, weightless 10% o'clock heat decomposition temperature Td
10: 284.93 ℃, weightless 50% o'clock heat decomposition temperature Td
50: 321.23 ℃, shock strength: 4.32kJ/m
2, tensile strength: 58.75MPa
Embodiment 14-17:
Operation is with embodiment 8, and difference is that employed heat-proof modifier is synthetic by embodiment 7.The consumption of heat-proof modifier is respectively 20.0g, 40.0g, 60.0g and 80.0g among the embodiment 14-17, PVC consumption 200.0g, 5.0g Jing Xi-8831, calcium stearate 1.6g, stearyl alcohol 1.6g.
Thermal characteristics and the mechanical property of the heat-proof modifier blending and modifying PVC of the different umbers of table 4
| Numbering | The consumption of heat-proof modifier (g) | Vicat softening point (℃) | Initial heat decomposition temperature (Td 10℃) | Heat decomposition temperature (Td 50℃) | Shock strength (kJ/m 2) | Tensile strength (Mpa) |
| Embodiment 14 embodiment 15 embodiment 16 embodiment 17 | 20 40 60 80 | 88.0 91.2 96.3 98.6 | 285.77 288.00 288.84 289.40 | 325.10 336.70 345.52 354.18 | 2.66 3.38 2.24 1.76 | 59.86 60.71 60.45 59.66 |
Annotate: the Vicat softening point of pure PVC is 82.9 ℃, weightless 10% o'clock heat decomposition temperature Td
10: 284.93 ℃, weightless 50% o'clock heat decomposition temperature Td
50: 321.23 ℃, shock strength: 4.32kJ/m
2, tensile strength: 58.75MPa
In sum, the consumption of toxilic acid list ten diester lanthanums is 5.5 parts in polymkeric substance, when N-cyclohexyl maleimide consumption is 10 parts, use this tetrapolymer and 100 parts of PVC blend of 20 parts, the Vicat softening point of gained blending and modifying PVC has improved 4.7 ℃ than pure PVC, initial heat decomposition temperature (temperature during thermal weight loss 10%) has improved 6.70 ℃ than pure PVC, temperature during thermal weight loss 50% is compared with pure PVC and is improved about 17.31 ℃, and shock strength, tensile strength are compared with pure PVC and improved 1.62% and 3.35% respectively.
Claims (3)
1. N-substituted maleimide heat-resistance modifier that contains rare earth is characterized by as follows and makes:
The composition quality umber
Monomer:
N-substituted maleimide amine 10
Toxilic acid monoester rare earth 5～25
Methyl methacrylate 10～70
Vinylbenzene 10～60
Initiator: 2～4 ‰ of Potassium Persulphate monomer total amount
Emulsifying agent: 2～6% of sodium lauryl sulphate monomer total amount
200～800% of deionized water monomer total amount
N-substituted maleimide amine recited above is specially: N-cyclohexyl maleimide or N-phenylmaleimide;
(1) raw material is handled: methyl methacrylate and vinylbenzene are all removed stopper through the underpressure distillation purifying in the above used monomer;
(2) preparation of heat-proof modifier: by top proportioning, agitator is being housed, thermometer, in the reactor of reflux condensing tube, add entry, emulsifying agent, feed nitrogen simultaneously, heating in water bath to 75 ℃, add initiator, begin dropping by constant pressure funnel and consist of N-substituted maleimide amine, the toxilic acid monoester rare earth, methyl methacrylate and cinnamic mix monomer, dripped monomer in 1-2 hour, continue heating and make system be warmed up to 80 ℃, reaction 1-2 hour is warmed up to 85 ℃ again, reaction 0.5-1 hour, use 18 water alum liquor breakdown of emulsion then, washing, oven dry, obtain the white powder solid, promptly contain the N-substituted maleimide heat-resistance modifier of rare earth.
2. the N-substituted maleimide heat-resistance modifier that contains rare earth as claimed in claim 1 is characterized by described toxilic acid monoester rare earth and is: toxilic acid list ten diester lanthanums, toxilic acid list ten diester ceriums or toxilic acid list ten diester neodymiums.
3. the application that contains the N-substituted maleimide heat-resistance modifier of rare earth as claimed in claim 1 is characterized by this N-substituted maleimide heat-resistance modifier as the thermo-stabilizer that improves the PVC thermostability, and blending and modifying PVC preparation process is as follows:
The composition quality umber
PVC 100
Gained heat-proof modifier 10-40 in the claim 1
Jing Xi-8,831 2.5
Calcium stearate 0.8
Stearyl alcohol 0.8
According to said ratio, with mixing on two roll plastic mixing mill after each component high-speed mixing of blending and modifying PVC, two roll temperatures obtain flaky material between 160-180 ℃, then between 170-200 ℃, being pressed into smooth sheet material on the plastic product hydraulic press, at last by omnipotent sampling machine sample preparation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101501888A CN100549050C (en) | 2007-11-16 | 2007-11-16 | A kind of N-substituted maleimide heat-resistance modifier that contains rare earth and its production and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101501888A CN100549050C (en) | 2007-11-16 | 2007-11-16 | A kind of N-substituted maleimide heat-resistance modifier that contains rare earth and its production and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101186671A true CN101186671A (en) | 2008-05-28 |
| CN100549050C CN100549050C (en) | 2009-10-14 |
Family
ID=39479314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007101501888A Expired - Fee Related CN100549050C (en) | 2007-11-16 | 2007-11-16 | A kind of N-substituted maleimide heat-resistance modifier that contains rare earth and its production and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100549050C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492302A (en) * | 2011-12-07 | 2012-06-13 | 山东科技大学 | Modified asphalt, and preparation method and use thereof |
| CN106995574A (en) * | 2017-05-16 | 2017-08-01 | 黑龙江林海华安新材料股份有限公司 | A kind of PVC product special assistant and its methods for making and using same |
| CN113603994A (en) * | 2021-07-21 | 2021-11-05 | 佳易容聚合物(上海)有限公司 | High-thermal-oxygen-stability high-heat-resistance spraying-free PMMA/ASA alloy resin composition and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3255330B2 (en) * | 1994-05-27 | 2002-02-12 | 電気化学工業株式会社 | Method for producing thermoplastic resin |
| CN1244674C (en) * | 2003-10-25 | 2006-03-08 | 福州大学 | Method for fabricating thermal stablilizer made from wool ester, rare earth in use for PVC |
| CN1308392C (en) * | 2003-11-27 | 2007-04-04 | 衡水精信化工有限公司 | Preparation method and application for composite rare-earth stabilizer for PVC profiled bar |
-
2007
- 2007-11-16 CN CNB2007101501888A patent/CN100549050C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492302A (en) * | 2011-12-07 | 2012-06-13 | 山东科技大学 | Modified asphalt, and preparation method and use thereof |
| CN102492302B (en) * | 2011-12-07 | 2014-04-23 | 山东科技大学 | Modified asphalt, and preparation method and use thereof |
| CN106995574A (en) * | 2017-05-16 | 2017-08-01 | 黑龙江林海华安新材料股份有限公司 | A kind of PVC product special assistant and its methods for making and using same |
| CN113603994A (en) * | 2021-07-21 | 2021-11-05 | 佳易容聚合物(上海)有限公司 | High-thermal-oxygen-stability high-heat-resistance spraying-free PMMA/ASA alloy resin composition and preparation method thereof |
| CN113603994B (en) * | 2021-07-21 | 2022-10-04 | 佳易容聚合物(上海)有限公司 | High-thermal-oxidative-stability high-heat-resistance spraying-free PMMA/ASA alloy resin composition and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100549050C (en) | 2009-10-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101302277B (en) | Functional fabric waterproof stiffener and preparation technology thereof | |
| CN101708973A (en) | Water-plastic retaining polycarboxylic acid water reducer and method for preparing same | |
| CN102659989A (en) | Preparation method of low-cost concrete polycarboxylic acid water reducing agent | |
| CN103467672B (en) | Waterborne organic silicon modified epoxy and preparation method thereof | |
| CN101864119B (en) | Preparation method of polyacrylic ester/montmorillonoid composite material | |
| CN100372874C (en) | Chlorinated polyethylene with high maximum elongation, and preparation process and application thereof | |
| CN104446089B (en) | A kind of concrete based on clay mineral flocculation resistance mud agent and preparation method thereof | |
| CN100549050C (en) | A kind of N-substituted maleimide heat-resistance modifier that contains rare earth and its production and application | |
| CN104017323A (en) | ABS/PVC blend alloy and preparation method thereof | |
| CN103130962B (en) | Chlorinated polyethylene rubber, butyl acrylate, acrylonitrile, N phenyl maleimide graft copolymer and preparation method thereof | |
| CN106939160A (en) | A kind of high mineralization water quality clean fracturing fluid | |
| CN102643383A (en) | Preparation method of raw oil-extended alkyl acrylate copolymer (ACM) | |
| JPS59120608A (en) | Rubber composition of improved vulcanizability | |
| CN102414264B (en) | Processability improver for foam molding and vinyl chloride resin composition containing same | |
| CN103265780A (en) | Chlorinated polyvinylchloride mixing material | |
| CN101544719B (en) | Method for producing chlorinated polyvinyl chloride processing modified adjuvant | |
| CN102093522B (en) | Polycarboxylic acid, use thereof and water reducer containing same | |
| Zhang et al. | Acrylonitrile‐Styrene‐Acrylate Particles with Different Microstructure for Improving the Toughness of Poly (styrene‐co‐acrylonitrile) Resin | |
| CN104193879A (en) | Melt reinforcing agent with functional group as well as preparation and application of melt reinforcing agent | |
| CN100425628C (en) | Preparation method of heat-proof modifier for uniform copolymerization | |
| JP2006265407A (en) | Transparent resin composition excellent in surface hardness and transparent resin molded product obtained by molding the resin composition | |
| CN106496443B (en) | A kind of polycarboxylate water-reducer masterbatch of sulfonic acid phosphate double-strand transferance | |
| CN101560281B (en) | EPM-g-MAN toughener and preparation method thereof as well as engineering plastics AEMS | |
| CN106188557B (en) | The method of unsaturated halogenated hydrocarbons copolymerized grafting cationic side chain preparation highly resistance chamotte mould polycarboxylate dispersant | |
| CN1357557A (en) | Production process of impact-resisting and heat resistant copolymerized resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20091014 Termination date: 20131116 |