CN102030959A - Silane cross-linked dynamically-vulcanized thermoplastic elastomer - Google Patents
Silane cross-linked dynamically-vulcanized thermoplastic elastomer Download PDFInfo
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- CN102030959A CN102030959A CN2010106125290A CN201010612529A CN102030959A CN 102030959 A CN102030959 A CN 102030959A CN 2010106125290 A CN2010106125290 A CN 2010106125290A CN 201010612529 A CN201010612529 A CN 201010612529A CN 102030959 A CN102030959 A CN 102030959A
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- thermoplastic elastomer
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- silane
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
Abstract
The invention relates to the technical field of thermoplastic elastomer materials, in particular to a silane cross-linked dynamically-vulcanized thermoplastic elastomer and a preparation method thereof. The elastomer comprises the following components in percentage by weight: 27 to 75 percent of silane-grafted elastomer, 20 to 70 percent of polyolefine resin, 0.1 to 0.3 percent of cross-linked catalyst, 0.5 to 2 percent of water producing agent, 0.1 to 0.5 percent of antioxidant and 0.2 to 0.5 percent of lubricant and is prepared by a reactive double-screw extruder. The influence of the conventional cross-linked system on the performance of the dynamically-vulcanized thermoplastic elastomer can be avoided.
Description
Technical field
The present invention relates to a kind of thermoplastic elastic material, particularly a kind of dynamic vulcanization thermoplastic elastomer with crosslinked with silicane.
Background technology
Dynamic vulcanization thermoplastic elastomer is in the seventies appearance in last century.Its notable feature be rubber phase in the screw mixes extrusion crosslinked and with tiny particles dispersed in thermoplastics, the working method of this analog thermoplastic elastomer available heat thermoplastic plastic is processed, and has the characteristic of rubber in very wide temperature range.Therefore, this class material has purposes widely in fields such as automobile, electronics, electrical equipment, building, packing.
In the prior art, the dynamic vulcanization thermoplastic elastomer preparation mainly concentrates on dynamic vulcanization method and prepares the EPDM/PP blending thermoplastic elastomer, three kinds of vulcanization systems generally commonly used: (1) sulfur sulfide system (2) peroxide vulcanizing system (3) phenolic resin vulcanization system.U.S. Mengshan all (Monsanto) is the company that obtains the dynamic vulcanization thermoplastic elastomer patent the earliest, and its U.S. Pat 4130535 and US4311628 are that linking agent prepares thermoplastic ethylene-propylene rubber/polyolefine elastomer with sulphur and resol respectively.What application number was that 200310106228.0 Chinese patent proposes is to be that linking agent prepares fire retardant EPT rubber/thermoplastic elastomer with resol.Application number is that 200710170562.0 Chinese patent proposes with the organo-peroxide is that linking agent prepares the elastomeric method of a kind of high quality dynamic vulcanization thermoplastic.Although more than various thermoplastic elastomers form and technology is distinguished to some extent, performance has their own characteristics each, yet, all these thermoplastic elastomers exist in the preparation extrusion owing to shear and blended energy and heat release are one of crosslinked or both cause part " hot spot ", cause the degraded of thermoplastic resin or rubber, undesirable reaction perhaps takes place, and causes the loss of the finished product performance.
Summary of the invention
In order to address the above problem, one of purpose of the present invention is, a kind of thermoplastic elastomer with the crosslinked with silicane preparation is provided, and can overcome traditional cross-linking system to the dynamic vulcanization thermoplastic elastomer Effect on Performance.
Another object of the present invention is, described process for preparation of thermoplastic elastomer with the crosslinked with silicane preparation is provided; This is invented, and not only preparation technology is simple, and with low cost.
The present invention is achieved through the following technical solutions:
A kind of dynamic vulcanization thermoplastic elastomer of crosslinked with silicane comprises the following raw material that calculates by mass ratio:
Silane grafting elastomerics 27%～75%
Polyolefin resin 20%～70%
Crosslinking catalyst 0.1%～0.3%
Produce aqua 0.5%～2%
Oxidation inhibitor 0.1%～0.5%
Lubricant 0.2%～0.5%.
Wherein, described silane grafting elastomerics comprises the following raw material that calculates by mass ratio:
100 parts on ethylene copolymer elastomerics
0.5～5 part in silane
0.05～1 part of peroxide initiator
0.1～0.5 part in oxidation inhibitor
0.2～0.5 part of lubricant.
Described ethylene copolymer elastomerics is the one or more combination thing in ethylene-propylene rubber(EPR), terpolymer EP rubber, ethylene-octene copolymer or the ethylene-vinyl acetate copolymer.
Described silane is the one or more combination thing in vinyltrimethoxy silane, vinyltriethoxysilane, vinyl methoxy ethoxy silane or the methacryloxypropyl triethoxyl silane.
Described peroxide initiator is dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2, the one or more combination thing in the 5-di-t-butyl hexane peroxide.
Described oxidation inhibitor is four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester or β-positive octadecanol esters of (3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid.
Described oxidation inhibitor is four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester or β-(3, the 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid respectively with the compound of 1～2: 1 ratio of three [2, the 4-di-tert-butyl-phenyl] phosphorous acid ester.
Described polyolefin resin is one or more the mixture in new LDPE (film grade), linear low density polyethylene, high density polyethylene(HDPE) or the polypropylene.
Described crosslinking catalyst is the one or more combination thing in dibutyl tin laurate, toxilic acid dibutyl tin, lauric acid toxilic acid dibutyl tin or the Bis(lauroyloxy)dioctyltin.
Described product aqua is one or more the mixture in sodium-acetate, SODIUM PHOSPHATE, MONOBASIC or the gypsum.
Described lubricant is one or more the mixture in paraffin, polyethylene wax or the Poly Propylene Wax.
The method for preparing thermoplastic elastomer through dynamic vulcanization of crosslinked with silicane comprises being prepared as follows step:
A, preparation silane grafting elastomerics, get ethylene copolymer elastomerics, silane, peroxide initiator, oxidation inhibitor and lubricant at first by weight, even through high-speed mixing, extruding pelletization in reactive twin screw extruder then, pellet after thorough drying silane grafting elastomerics;
The dynamic vulcanization thermoplastic elastomer of B, preparation crosslinked with silicane, get silane grafting elastomerics, polyolefin resin, crosslinking catalyst, product aqua, oxidation inhibitor and lubricant by weight, even through high-speed mixing, extruding pelletization in reactive twin screw extruder makes final thermoplastic elastomer then.
The length-to-diameter ratio L/D of described reactive twin screw extruder is more than 42, and extrusion temperature is: 120 ℃～160 ℃ of feeding sections, 180 ℃～190 ℃ of compression sections, 190 ℃～210 ℃ of homogenizing zones, 200 ℃～220 ℃ of machine head port mould parts.
The present invention is counted by weight percentage, and comprises silane grafting elastomerics 27%～75%, polyolefin resin 20%～70%, crosslinking catalyst 0.1%～0.3%, produces aqua 0.5%～2%, oxidation inhibitor 0.1%～0.5%, lubricant 0.2%～0.5%; And be prepared and get by reactive twin screw extruder; The present invention can overcome traditional cross-linking system to the dynamic vulcanization thermoplastic elastomer Effect on Performance; Avoid preparing in the extrusion and to exist, cause the drawback of the loss of the finished product performance owing to shear and blended energy and heat release are one of crosslinked or both cause part " hot spot ", cause the degraded of thermoplastic resin or rubber or undesirable reaction takes place.
Concrete embodiment
The present invention is described in further detail below in conjunction with embodiment, understands the present invention to help those skilled in the art.
Embodiment 1
A kind of dynamic vulcanization thermoplastic elastomer of crosslinked with silicane comprises the following raw material that calculates by mass ratio:
Silane grafting elastomerics 30%; Polyolefin resin 68% (polyolefin resin is the composition of new LDPE (film grade) 2%, linear low density polyethylene 2%, high density polyethylene(HDPE) 10% and polypropylene 54%); Crosslinking catalyst 0.1%～0.3% (crosslinking catalyst is the composition of dibutyl tin laurate 0.1%, toxilic acid dibutyl tin 0.1% and lauric acid toxilic acid dibutyl tin 0.1%); Sodium-acetate 0.5%; Four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester 0.5%; Lubricant 0.5% (lubricant is the composition of paraffin 0.3%, polyethylene wax 0.1%, Poly Propylene Wax 0.1%).
Wherein, described silane grafting elastomerics comprises the following raw material that calculates by mass ratio: 100 parts in ethylene-propylene rubber(EPR); 0.5 part of vinyltrimethoxy silane; 1 part of peroxide initiator (peroxide initiator is 0.2 part of 0.2 part of a dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2, the composition that the 5-di-t-butyl hexane peroxide is 0.6 part); 00.5 part in oxidation inhibitor (oxidation inhibitor is the compound of 2: 1 ratios of four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester and three [2, the 4-di-tert-butyl-phenyl] phosphorous acid ester); 0.5 part of polyethylene wax.
The method for preparing thermoplastic elastomer through dynamic vulcanization of crosslinked with silicane comprises being prepared as follows step:
A, preparation silane grafting elastomerics, get ethylene copolymer elastomerics, silane, peroxide initiator, oxidation inhibitor and lubricant at first by weight, even through high-speed mixing, extruding pelletization in reactive twin screw extruder then, pellet after thorough drying silane grafting elastomerics;
The dynamic vulcanization thermoplastic elastomer of B, preparation crosslinked with silicane, get silane grafting elastomerics, polyolefin resin, crosslinking catalyst, product aqua, oxidation inhibitor and lubricant by weight, even through high-speed mixing, extruding pelletization in reactive twin screw extruder makes final thermoplastic elastomer then.
The length-to-diameter ratio L/D of described reactive twin screw extruder is more than 42, and extrusion temperature is: 160 ℃ of feeding sections, 180 ℃ of compression sections, 210 ℃ of homogenizing zones, 200 ℃ of machine head port mould parts; Screw speed is 400r/min
Embodiment 2
A kind of dynamic vulcanization thermoplastic elastomer of crosslinked with silicane comprises the following raw material that calculates by mass ratio:
Silane grafting elastomerics 75%; Polypropylene 23%; Crosslinking catalyst 0.2% (crosslinking catalyst is the composition of dibutyl tin laurate 0.1% and toxilic acid dibutyl tin 0.1%); Produce aqua 1.5% (producing aqua is the composition of sodium-acetate 0.1%, SODIUM PHOSPHATE, MONOBASIC 0.1%, gypsum 1.3%); β-positive octadecanol the ester 0.1% of (3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid; Polyethylene wax 0.2%.
Wherein, described silane grafting elastomerics comprises the following raw material that calculates by mass ratio: 100 parts on ethylene copolymer elastomerics (the ethylene copolymer elastomerics is the composition of 80 parts of 20 parts of ethylene-octene copolymers and ethylene-vinyl acetate copolymers); 1 part of vinyltrimethoxy silane; 0.2 part of peroxide initiator (peroxide initiator is 0.1 part of di-t-butyl peroxide and 2,5-dimethyl-2, the composition that the 5-di-t-butyl hexane peroxide is 0.1 part); 0.2 part in oxidation inhibitor (oxidation inhibitor is the compound of 1: 1 ratio of the β-positive octadecanol ester of (3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid and three [2, the 4-di-tert-butyl-phenyl] phosphorous acid ester); 0.3 part in paraffin.
The preparation method is with embodiment 1, and wherein, the extrusion temperature of described parallel dual-screw extruding machine is: 120 ℃ of feeding sections, and 200 ℃ of 190 ℃ of homogenizing zones in compression section, 220 ℃ of machine head port mould parts, screw speed is 100r/min.
Embodiment 3
A kind of dynamic vulcanization thermoplastic elastomer of crosslinked with silicane comprises the following raw material that calculates by mass ratio:
Silane grafting elastomerics 27%; New LDPE (film grade) 70%; Bis(lauroyloxy)dioctyltin 0.3%; Sodium-acetate 2%; β-positive octadecanol the ester 0.4% of (3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid; Poly Propylene Wax 0.5%.
Wherein, described silane grafting elastomerics comprises the following raw material that calculates by mass ratio: 100 parts in ethylene-propylene rubber(EPR); 2 parts in vinyl methoxy ethoxy silane, 0.8 part of di-t-butyl peroxide; Four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] 0.1 part of pentaerythritol ester, 0.4 part in paraffin.
The preparation method is with embodiment 1, and wherein, the extrusion temperature of described parallel dual-screw extruding machine is: 130 ℃ of feeding sections, and 206 ℃ of 182 ℃ of homogenizing zones in compression section, 208 ℃ of screw speeds of machine head port mould part are 180r/min.
Embodiment 4
A kind of dynamic vulcanization thermoplastic elastomer of crosslinked with silicane comprises the following raw material that calculates by mass ratio:
Silane grafting elastomerics 58%; High density polyethylene(HDPE) 40%; Dibutyl tin laurate 0.1%; SODIUM PHOSPHATE, MONOBASIC 0.5%; Four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester 0.5; Polyethylene wax 0.4%.
Wherein, described silane grafting elastomerics comprises the following raw material that calculates by mass ratio: 100 parts of ethylene-octene copolymers; 3 parts in vinyl methoxy ethoxy silane; 0.6 part of peroxide initiator (peroxide initiator is 0.3 part of di-t-butyl peroxide and 2,5-dimethyl-2, the composition that the 5-di-t-butyl hexane peroxide is 0.3 part); 0.4 part in oxidation inhibitor (compounds of 1.5: 1 ratios of the β-positive octadecanol ester of (3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid and three [2, the 4-di-tert-butyl-phenyl] phosphorous acid ester); 0.2 part in paraffin.
The preparation method is with embodiment 1, and wherein, the extrusion temperature of described parallel dual-screw extruding machine is: 160 ℃ of feeding sections, and 215 ℃ of 185 ℃ of homogenizing zones in compression section, 202 ℃ of screw speeds of machine head port mould part are 200r/min.
Embodiment 5
A kind of dynamic vulcanization thermoplastic elastomer of crosslinked with silicane comprises the following raw material that calculates by mass ratio:
Silane grafting elastomerics 70; New LDPE (film grade) 25.3%; Toxilic acid dibutyl tin 0.2%; Sodium-acetate 1%; Four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester 0.2%; Poly Propylene Wax 0.3%.
Wherein, described silane grafting elastomerics comprises the following raw material that calculates by mass ratio: 100 parts in ethylene-propylene rubber(EPR); 5 parts of methacryloxypropyl triethoxyl silanes; 0.05 part of dicumyl peroxide; 0.1 part of four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester; 0.2 part of ethylene waxes.
The preparation method is with embodiment 1, and wherein, the extrusion temperature of described parallel dual-screw extruding machine is: 160 ℃ of feeding sections, and 210 ℃ of 190 ℃ of homogenizing zones in compression section, 210 ℃ of screw speeds of machine head port mould part are 300r/min.
Embodiment 6
A kind of dynamic vulcanization thermoplastic elastomer of crosslinked with silicane comprises the following raw material that calculates by mass ratio:
Silane grafting elastomerics 40; High density polyethylene(HDPE) 67%; Toxilic acid dibutyl tin 0.3%; Sodium-acetate 2%; β-positive octadecanol the ester 0.5% of (3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid; Poly Propylene Wax 0.2%.
Wherein, described silane grafting elastomerics comprises the following raw material that calculates by mass ratio: 100 parts of ethylene-vinyl acetate copolymers; 5 parts of methacryloxypropyl triethoxyl silanes; 0.05 part of di-t-butyl peroxide; 0.1 part of the β-positive octadecanol ester of (3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid; 0.2 part in paraffin.
The preparation method is with embodiment 1, and wherein, the extrusion temperature of described parallel dual-screw extruding machine is: 130 ℃ of feeding sections, and 202 ℃ of 190 ℃ of homogenizing zones in compression section, 218 ℃ of screw speeds of machine head port mould part are 350r/min.
The foregoing description is preferred embodiment of the present invention, is not to be used for limiting the scope of the present invention, so all equivalences of being done with described feature of claim of the present invention and principle change or modify, all should be included within the claim scope of the present invention.
The product that obtains after testing, the gained performance data sees Table 1.
Table 1
As can be seen from Table 1, the present invention has overcome traditional cross-linking system to the dynamic vulcanization thermoplastic elastomer Effect on Performance, and the performance perameter of each side is all relatively good.
Claims (10)
1. the dynamic vulcanization thermoplastic elastomer of a crosslinked with silicane is characterized in that, comprises the following raw material that calculates by mass ratio:
Silane grafting elastomerics 27%～75%
Polyolefin resin 20%～70%
Crosslinking catalyst 0.1%～0.3%
Produce aqua 0.5%～2%
Oxidation inhibitor 0.1%～0.5%
Lubricant 0.2%～0.5%.
2. according to the dynamic vulcanization thermoplastic elastomer of the described crosslinked with silicane of claim 1, it is characterized in that described silane grafting elastomerics comprises the following raw material that calculates by mass ratio:
100 parts on ethylene copolymer elastomerics
0.5～5 part in silane
0.05～1 part of peroxide initiator
0.1～0.5 part in oxidation inhibitor
0.2～0.5 part of lubricant.
Described ethylene copolymer elastomerics is the one or more combination thing in ethylene-propylene rubber(EPR), terpolymer EP rubber, ethylene-octene copolymer or the ethylene-vinyl acetate copolymer.
Described silane is the one or more combination thing in vinyltrimethoxy silane, vinyltriethoxysilane, vinyl methoxy ethoxy silane or the methacryloxypropyl triethoxyl silane.
3. the dynamic vulcanization thermoplastic elastomer of crosslinked with silicane according to claim 2, it is characterized in that, described peroxide initiator is dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2, the one or more combination thing in the 5-di-t-butyl hexane peroxide.
4. the dynamic vulcanization thermoplastic elastomer of crosslinked with silicane according to claim 2, it is characterized in that, described oxidation inhibitor is four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester or β-positive octadecanol esters of (3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid.
5. the dynamic vulcanization thermoplastic elastomer of crosslinked with silicane according to claim 2, it is characterized in that, described oxidation inhibitor is four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester or β-(3, the 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid respectively with the compound of 1～2: 1 ratio of three [2, the 4-di-tert-butyl-phenyl] phosphorous acid ester.
6. the dynamic vulcanization thermoplastic elastomer of crosslinked with silicane according to claim 1 is characterized in that, described polyolefin resin is one or more the mixture in new LDPE (film grade), linear low density polyethylene, high density polyethylene(HDPE) or the polypropylene.
7. the dynamic vulcanization thermoplastic elastomer of crosslinked with silicane according to claim 1, it is characterized in that described crosslinking catalyst is the one or more combination thing in dibutyl tin laurate, toxilic acid dibutyl tin, lauric acid toxilic acid dibutyl tin or the Bis(lauroyloxy)dioctyltin.
8. the dynamic vulcanization thermoplastic elastomer of crosslinked with silicane according to claim 1 is characterized in that, described product aqua is one or more the mixture in sodium-acetate, SODIUM PHOSPHATE, MONOBASIC or the gypsum.
9. according to the dynamic vulcanization thermoplastic elastomer of any described crosslinked with silicane in claim 1 or 2, it is characterized in that described lubricant is one or more the mixture in paraffin, polyethylene wax or the Poly Propylene Wax.
10. the method for preparing thermoplastic elastomer through dynamic vulcanization of a crosslinked with silicane as claimed in claim 1 is characterized in that, comprises being prepared as follows step:
A, preparation silane grafting elastomerics, get ethylene copolymer elastomerics, silane, peroxide initiator, oxidation inhibitor and lubricant at first by weight, even through high-speed mixing, extruding pelletization in reactive twin screw extruder then, pellet after thorough drying silane grafting elastomerics;
The dynamic vulcanization thermoplastic elastomer of B, preparation crosslinked with silicane, get silane grafting elastomerics, polyolefin resin, crosslinking catalyst, product aqua, oxidation inhibitor and lubricant by weight, even through high-speed mixing, extruding pelletization in reactive twin screw extruder makes final thermoplastic elastomer then.
The extrusion temperature of described reactive twin screw extruder is: 120 ℃～160 ℃ of feeding sections, 180 ℃～190 ℃ of compression sections, 190 ℃～210 ℃ of homogenizing zones, 200 ℃～220 ℃ of machine head port mould parts.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432943A (en) * | 2011-10-17 | 2012-05-02 | 佛山市日丰企业有限公司 | Elastomer composition, elastomer hose and preparation method for elastomer hose |
| CN103172937A (en) * | 2013-04-11 | 2013-06-26 | 杭州恒标管业有限公司 | Special material for silicane grafted PPR (polypropylene random) pipe and preparation method thereof |
| CN105237881A (en) * | 2015-11-06 | 2016-01-13 | 沈阳化工大学 | Toughening modified recycled polypropylene micro-crosslinking master batch and preparation method thereof |
| CN106493811A (en) * | 2016-11-02 | 2017-03-15 | 广州精点高分子材料制品有限公司 | A kind of pottery wood and its manufacture method |
| CN106867107A (en) * | 2017-02-28 | 2017-06-20 | 山东道恩高分子材料股份有限公司 | A kind of low smell, injection skin material of low-friction coefficient and preparation method thereof |
| CN110066463A (en) * | 2019-05-22 | 2019-07-30 | 青岛海尔新材料研发有限公司 | A kind of PP composite material of autoreaction toughening |
| CN111454668A (en) * | 2020-04-13 | 2020-07-28 | 杭州福斯特应用材料股份有限公司 | Co-extrusion adhesive film, solar cell module and double-layer glass |
| CN114672131A (en) * | 2022-05-16 | 2022-06-28 | 南京工程学院 | Automatic micro-crosslinking halogen-free flame-retardant thermoplastic elastomer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102432943A (en) * | 2011-10-17 | 2012-05-02 | 佛山市日丰企业有限公司 | Elastomer composition, elastomer hose and preparation method for elastomer hose |
| CN103172937A (en) * | 2013-04-11 | 2013-06-26 | 杭州恒标管业有限公司 | Special material for silicane grafted PPR (polypropylene random) pipe and preparation method thereof |
| CN103172937B (en) * | 2013-04-11 | 2015-10-28 | 杭州恒标管业有限公司 | A kind of Silane Grafted PPR pipe PP Pipe Compound and preparation method thereof |
| CN105237881A (en) * | 2015-11-06 | 2016-01-13 | 沈阳化工大学 | Toughening modified recycled polypropylene micro-crosslinking master batch and preparation method thereof |
| CN106493811A (en) * | 2016-11-02 | 2017-03-15 | 广州精点高分子材料制品有限公司 | A kind of pottery wood and its manufacture method |
| CN106867107A (en) * | 2017-02-28 | 2017-06-20 | 山东道恩高分子材料股份有限公司 | A kind of low smell, injection skin material of low-friction coefficient and preparation method thereof |
| CN110066463A (en) * | 2019-05-22 | 2019-07-30 | 青岛海尔新材料研发有限公司 | A kind of PP composite material of autoreaction toughening |
| CN110066463B (en) * | 2019-05-22 | 2022-01-18 | 青岛海纳新材料有限公司 | Self-reaction toughened polypropylene composite material |
| CN111454668A (en) * | 2020-04-13 | 2020-07-28 | 杭州福斯特应用材料股份有限公司 | Co-extrusion adhesive film, solar cell module and double-layer glass |
| CN111454668B (en) * | 2020-04-13 | 2022-04-15 | 杭州福斯特应用材料股份有限公司 | Co-extrusion adhesive film, solar cell module and double-layer glass |
| CN114672131A (en) * | 2022-05-16 | 2022-06-28 | 南京工程学院 | Automatic micro-crosslinking halogen-free flame-retardant thermoplastic elastomer and preparation method thereof |
| CN114672131B (en) * | 2022-05-16 | 2023-11-28 | 南京工程学院 | Automatic micro-crosslinking halogen-free flame-retardant thermoplastic elastomer and preparation method thereof |
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