CN1869119A - Preparation method of partly cross-linked dystectic strength polypropylene - Google Patents
Preparation method of partly cross-linked dystectic strength polypropylene Download PDFInfo
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- CN1869119A CN1869119A CN 200510043675 CN200510043675A CN1869119A CN 1869119 A CN1869119 A CN 1869119A CN 200510043675 CN200510043675 CN 200510043675 CN 200510043675 A CN200510043675 A CN 200510043675A CN 1869119 A CN1869119 A CN 1869119A
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Abstract
A partially cross-linked polypropene with high strength of its fused body is prepared through mixing polypropene, unsaturated silane, alcoholyzing agent of silane, organically modified laminar silicate, silicon-alcohol condensate, catalyst, organic peroxide and graft assistant, screw extruding out, and granulating.
Description
Technical field:
The present invention relates to improve with the reaction extrusion molding Technology of the melt strength of alfon and multipolymer, particularly a kind of one step of usefulness silane thermal decomposition process prepares the method for partly cross-linked dystectic strength polypropylene, belongs to polymeric material field.
Technical background:
Polypropylene has that the source is wide, light weight, easily reclaim and degrade (if desired), superiority such as mechanical property is superior, high temperature resistant, tasteless odorless, favored by people, its application quantity comes the front three of plastic material.Yet, low, the poor toughness of melt strength of polypropylene, thus limited its range of application greatly, especially foaming, thermoforming, blowing, showing the drawback that it is serious when extruding moulding such as coating.Develop high melt strength, propylene and be the valid approach that overcomes above-mentioned drawback.In recent years, numerous countries drop into a large amount of manpower and materials and carry out the research of this aspect, have obtained gratifying progress.
Summary is got up, and the method that improves melt strength of polypropylene at present mainly contains three kinds: the one, and the directly synthetic polypropylene that contains long-chain branch, it is big that this method prepares difficulty, and investment is big, only has country such as Belgium to have such technology at present; The 2nd, with blend such as polypropylene and polyethylene and elastomericss, the drawback of this method is when having improved melt strength of polypropylene, and its thermotolerance and readily degradable also significantly reduce; It three is that existing polypropylene is carried out grafting or partial cross-linked by different methods, and this class methods less investment, production technique are simple relatively, can keep the various performances of polypropylene itself simultaneously again.
Have many polypropylene grafted and partial cross-linked methods of carrying out at present.U.S. Pat 5578682 has disclosed and has been used in combination the melt strength that various how unsaturated linking agent (as the bismaleimide sulfonamide derivatives) and radical initiator improve various polymkeric substance.
Borsig etc. described by with peroxide treatment in batches modified polypropene make the method (Borsig, E., Fiedlerova, A., Lazar, M.J.Macromol.Sic.Chem., 1981, A16,513) of crosslinked polypropylene.Chinese patent (publication number CN1291213A) provide a kind of method that improves melt strength of polypropylene, and it is under the monomeric effect of vinyl compound, by superoxide initiation grafting and crosslinked.Aforesaid method needs a large amount of superoxide.
Chinese patent (publication number 1346843) has disclosed a kind of method for preparing high melt strength polyolefin (polypropylene and poly mixture) by cross-linking radiation; This method since blending polyethylene, changed polyacrylic composition, easily cause declines such as the thermotolerance of polypropylene own, simultaneously cross-linking radiation is subject to the restriction of the irradiation degree of depth and needs protection of inert gas.
H.HUANG etc. (Journal of Applied Polymer Science, 2000, Vol.78 1233-1238) has described a kind of multistep processes and has prepared the Silane Crosslinked Polypropylene method.Promptly be grafting agent with the unsaturated silane, as silane grafting auxiliary agent, (DCP or BPO) is initiator with superoxide with vinylbenzene, and dibutyl tin dilaurate is a crosslinking coagent, reacts on testing with Haake TW100 twin screw extruder and extrudes.Its basic step is: (A) with after polypropylene and unsaturated silane, vinylbenzene, peroxide initiator (DCP or the BPO) premix, in the feeding forcing machine, react extruding pelletization about 190 ℃, prepare silane grafted polyacrylate, this material is expected as A.(B) with after 4 parts of dibutyl tin dilaurate and the 100 parts of polypropylene premix, extruding pelletization is expected as B on above-mentioned twin screw extruder.(C) 100 parts of A are expected expect in above-mentioned forcing machine, to mix granulation again after dried the mixing, prepare the silane grafted polyacrylate particle that contains crosslinking coagent with 5 parts of B.(D) above-mentioned particle fusion is pressed into the thick sheet of 1mm, puts into boiling water after shredding and boiled 6 hours, prepare the highest gel content near 50% partial cross-linked polypropylene.This method needs multistep could realize Crosslinking of Polypropylene, and technology is quite complicated.
Summary of the invention:
The objective of the invention is to overcome the shortcoming that exists in the prior art, provide an a kind of step silane thermal decomposition process to prepare the method for partly cross-linked dystectic strength polypropylene.The realization of the object of the invention, it is characterized in that earlier polypropylene, unsaturated silane and alcoholysis agent, organic modified sheet silicate, silanol contract and catalyzer, organic peroxide evocating agent, grafting auxiliary agent are pre-mixed, feed mixture in the screw extrusion press together again, under the conditions such as temperature, rotating speed and feed rate of control, melt extrude and granulation, the partly cross-linked dystectic strength polypropylene product is made in the grafting of one step realization polypropylene and silane and crosslinked.This method technology is simple especially, less investment, and the polypropylene that can prepare different gel contents and melt strength by the adjustment of composition of raw materials and technology is to satisfy as polypropylene extrusion foaming, thermoforming, film blowing, to extrude the demand of different product producing process such as coating.
The preparating mechanism of the inventive method is characterised in that: unsaturated silane with polypropylene grafted before, at first form unsaturated silanol with alcoholysis agent effect, and under the certain temperature of forcing machine feed zone, organic modified sheet silicate and (or) condensation takes place down in the effect of silicon alcohol condensation catalyst, generation has the silane condensation thing of many unsaturated groups.Along with the rising of temperature, peroxide initiator decomposes, and causes the reaction of polypropylene and silane condensation thing, realizes that a step is crosslinked.
The proportioning raw materials of the preparation of the partly cross-linked dystectic strength polypropylene that the present invention relates to is formed: (A) polypropylene 100 weight parts, (B) unsaturated silane 0.008-10 weight part, (C) alcoholysis agent 0.005-8 weight part, (D) silicon alcohol condensation catalyst 0-5 weight part, (E) organic modified sheet silicate 0.1-6 weight part, (F) organic peroxide evocating agent 0.005-5 weight part, (G) grafting auxiliary agent 0.03-10 weight part.
Screw extrusion press of the present invention comprises the screw extrusion press of single screw extrusion machine, twin screw extruder, multiple screw extruder or other form.The length-to-diameter ratio of forcing machine is preferably in 25-60 in the 15-100 scope; Rotating speed is 10-500 rev/min, generally at 20-400 rev/min; Controllable temperature is at 50-500 ℃, 60-350 ℃ more fortunately; Can adopt a plurality of charging openings in case of necessity, additional side is to drawing-in device, liquid quantitative feeding device, vacuum pumping hardware etc.Each section temperature that realizes the forcing machine in the process of the present invention should be controlled at 50-250 ℃, preferably is controlled at 60-230 ℃, and wherein the temperature of feed zone is lower than the temperature of other each section.
Polypropylene of the present invention is homopolymer polypropylene or multipolymer or its both blend.
Unsaturated silane of the present invention is meant that all contain the silane of unsaturated group, comprise vinyltrimethoxy silane (A-171), vinyltriethoxysilane (A-151), vinyl ('beta '-methoxy oxyethyl group) silane (A-172), vinyl-triacetoxysilane (SH-6075), γ-propyl methacrylate base silane (A-174), vinyl trichloro silane (A-150), γ-[n-(β-isobutyl-acyl-oxygen ethyl)-n, n-alkyl dimethyl ammonium chloride] propyl trimethoxy silicane, styryl two aminopropyl silanes etc.
Alcoholysis agent of the present invention is water and aquo compound or the compound that at high temperature can form water etc., high temperature can discharge down the compound of water, comprises the derivative etc. of polyvinyl alcohol, beta-hydroxy acid and this alcohol acid of the aluminium hydroxide of being with crystal water, gypsum, short-chain branch; The compound of suction such as calcium chloride etc.; The compound of water generation reaction and composition comprise organic acid and nonhygroscopic metal oxide at a certain temperature, and organic acid comprises stearic acid, hexanodioic acid etc.; Metal oxide comprises tin protoxide, zinc oxide etc.Wherein find preferably water and aquo compound.
Organic modified sheet silicate of the present invention is meant the layered silicate of handling by methods such as ion-exchanges with organic intercalation agent, dispersion medium etc., or realizes the layered silicate that organises with additive method; Wherein layered silicate is clay, carclazyte, polynite or Meccah stone etc.; Organic intercalation agent comprises alkyl amine, the alkylammonium salt, and alcamines, several lactan, lauric acid amine, phenyl-ethyl amine, Ursol D etc., dispersion medium comprises water, alcohols, ketone etc.
Organic peroxide evocating agent of the present invention comprises tertbutyl peroxide, 1,1,3,3,-tetramethyl--butylhydroperoxide, cumyl hydroperoxide, p-Methylisopropylbenzene base hydrogen peroxide, di-isopropylbenzene hydroperoxide, 2,5-dimethyl-2,5-two hydroperoxy hexanes, the cyclic group ketone peroxide, methyl cyclic group ketone peroxide, 3,3,5-trimethylammonium cyclic group ketone peroxide, ditertiary butyl peroxide, dicumyl peroxide, tert butyl isopropyl benzene peroxide, diacetyl peroxide, dipropyonyl peroxide, peroxidation two butyryl, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, two (3,5, the 5-trimethyl acetyl) superoxide, dibenzoyl peroxide etc.
Silicon alcohol condensation catalyst of the present invention, its effect be unsaturated silanol and polypropylene grafted before promote it to contract and, form the silane condensation thing that has many unsaturated groups; Can be organometallic compound, as dibutyltin dilaurate, dibutyl tin two lauric acid salt, alkyl titanic acid ester, octene tin, lead octoate 36 etc.; Also can be mineral acid, lipid acid etc.
Grafting auxiliary agent of the present invention refers to assists to realize silane and polyacrylic grafting, stops polypropylene molecular chain that the auxiliary agent of degraded takes place simultaneously; Such grafting auxiliary agent comprises oxazoline, vinyl pyridine, Vinylstyrene, vinylbenzene etc.
Specific embodiments:
Embodiment 1:
The starting material component: component (A) is 100 parts of homo-polypropylene, and Qilu Petrochemical company produces, and the trade mark is T30S.Component (B) is 0.3 part of γ-propyl methacrylate base silane (A-174); Component (C) is 3.0 parts of distilled water; Component (D) is 0 part of dibutyltin dilaurate; Component (E) is 1.0 parts of organic modified sheet silicates; Component (F) is 0.36 part of dibenzoyl peroxide (BPO); Component (G) is 0.135 part of vinylbenzene.
The preparation of organic modified sheet silicate: after with ball mill layered silicate being ground, with 325 purpose sieve, the layered silicate that obtains from exchange capacity be 96.4meq/100g.The 1.8g amino dodecane is dissolved in 1000ml60 ℃ the 0.01M hydrochloric acid and makes solution, the 10g layered silicate is added in this solution gradually, the suspension thermal agitation 3h that obtains, repeatedly wash with deionized water again, at 80 ℃ of following vacuum-drying 12h, grind after 325 purpose sieve just obtain organic modified sheet silicate again after the filtered residue.
Screw extrusion press structure and function: the forcing machine that is adopted is for rotating cord wood engagement type twin screw extruder in the same way, and screw diameter is 35mm, and length-to-diameter ratio is 32, and seven sections heating temperature controls are adopted in speed control by frequency variation, carry out vacuum exhaust the 6th section of forcing machine.
The preparation of partly cross-linked dystectic strength polypropylene: use high-speed mixer, above-mentioned all components is mixed, in twin screw extruder, react extruding pelletization then and promptly make product of the present invention.120 rev/mins of control forcing machine rotating speeds, each section temperature is controlled to be from the spout to the head: 50 ℃, 120 ℃, 180 ℃, 190 ℃, 195 ℃, 195 ℃, 185 ℃.
Embodiment 2:
The starting material component: component (A) is 100 parts of homo-polypropylene, and Qilu Petrochemical company produces, and the trade mark is T30S.Component (B) is 0.6 part of γ-propyl methacrylate base silane (A-174); Component (C) is 6.0 parts of distilled water; Component (D) is 0 part of dibutyltin dilaurate; Component (E) is 2.0 parts of organic modified sheet silicates; Component (F) is 0.36 part of dibenzoyl peroxide (BPO); Component (G) is 0.270 part of vinylbenzene.
All the other operation stepss, method are all with embodiment 1.
Embodiment 3:
The starting material component: component (A) is 100 parts of homo-polypropylene, and Qilu Petrochemical company produces, and the trade mark is T30S.Component (B) is 0.9 part of γ-propyl methacrylate base silane (A-174); Component (C) is 9.0 parts of distilled water; Component (D) is 0 part of dibutyltin dilaurate; Component (E) is 3.0 parts of organic modified sheet silicates; Component (F) is 0.36 part of dibenzoyl peroxide (BPO); Component (G) is 0.405 part of vinylbenzene.
All the other operation stepss, method are all with embodiment 1.
Embodiment 4:
The starting material component: component (A) is 100 parts of homo-polypropylene, and Qilu Petrochemical company produces, and the trade mark is T30S.Component (B) is 0.9 part of γ-propyl methacrylate base silane (A-174); Component (C) is 9.0 parts of distilled water; Component (D) is 0.3 part of dibutyltin dilaurate; Component (E) is 3.0 parts of organic modified sheet silicates; Component (F) is 0.36 part of dibenzoyl peroxide (BPO); Component (G) is 0.405 part of vinylbenzene.
All the other operation stepss, method are all with embodiment 1.
The product that obtains is carried out performance tests such as gel content, melt strength, is Comparative Examples with the polypropylene, and result and composition of raw materials see Table 1.
The test of gel content: product is hot pressed into thin slice about 1mm, is cut into fragment again less than the 2mm size.Accurately institute's sample thief about weighing 0.5g is wrapped with 200 purpose copper mesh, and the extracting of usefulness dimethylbenzene is 12 hours in Soxhlet extractor, then sample is moved in the vacuum drying oven, is dried to weight in 80 ℃, is the gel weight of sample.Gel content accounts for the percentage calculation of sample starting weight according to gel weight.The extracting three times at least of every kind of sample calculates average gel content with drawing a conclusion.
The test of melt strength: 010.1 type " Rheotens " the melt strength experimental machine test that melt strength adopts German Gottfert Werkstoff-Prufmaschinen company to provide.Experiment condition is: 190 ℃ of head temperatures, and forcing machine discharging speed is 4 gram/minute, acceleration is 1.2 cels
2, stretching distance is 210 millimeters.
One crosslinked affirmation of step: whether realized that in order to confirm prepared product a step is crosslinked, product is hot pressed into thin slice about 1mm, be cut into fragment again less than the 2mm size.Put it into and boil 6 hours in the water.Survey its gel content then, and with poach before compare.
The test of foam performance and result: the partly cross-linked dystectic strength polypropylene with the inventive method preparation has carried out the foam performance test, with general AC (Cellmic C 121) whipping agent and corresponding frothing aid thereof, by twin screw extruder extrusion foaming sheet material of the present invention.The microphotograph result displayed shows, with partly cross-linked dystectic strength polypropylene of the present invention can prepare have even closed pore, density is at the 0.8-0.05 gram per centimeter
3Foam material.
Table 1
| Comparative Examples 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Polypropylene (T30S, weight part) γ-propyl methacrylate base silane (weight part) distilled water (weight part) dibutyltin dilaurate (weight part) organic modified sheet silicate (weight part) dibenzoyl peroxide (BPO, weight part) vinylbenzene (weight part) melt flow rate (MFR) (restrains/10 minutes, 230 ℃, 2.16 kilogram) melt strength (Mpa) gel content (%) heat-drawn wire (℃, 0.45Mpa) gel content (%) behind the poach | 100 0 0 0 0 0 0 3.84 2.6 0 123.5 0 | 100 0.3 3.0 0 1.0 0.36 0.135 0.58 10.6 22.3 131.7 22.1 | 100 0.6 6.0 0 2.0 0.36 0.270 0.196 15.3 34.6 136.0 34.5 | 100 0.9 9.0 0 3.0 0.36 0.405 0.08 18.2 45.0 142.2 45.2 | 100 0.9 9.0 0.3 3.0 0.36 0.405 0.08 18.6 45.3 141.8 45.6 |
Claims (11)
1, a kind of preparation method of partly cross-linked dystectic strength polypropylene, it is characterized in that earlier polypropylene, unsaturated silane and alcoholysis agent, organic modified sheet silicate, silanol contract and catalyzer, organic peroxide evocating agent, grafting auxiliary agent are pre-mixed, feed mixture in the screw extrusion press together again, under temperature, rotating speed and the feed rate condition of control, melt extrude and granulation, partly cross-linked dystectic strength polypropylene is made in the grafting of one step realization polypropylene and silane and crosslinked.
2, the preparation method of partly cross-linked dystectic strength polypropylene according to claim 1, it is characterized in that the proportioning raw materials composition is: (A) polypropylene 100 weight parts, (B) unsaturated silane 0.008-10 weight part, (C) alcoholysis agent 0.005-8 weight part, (D) silicon alcohol condensation catalyst 0-5 weight part, (E) organic modified sheet silicate 0.1-6 weight part, (F) organic peroxide evocating agent 0.005-5 weight part, (G) grafting auxiliary agent 0.03-10 weight part.
3, the preparation method of partly cross-linked dystectic strength polypropylene according to claim 1 is characterized in that described screw extrusion press comprises the screw extrusion press of single screw extrusion machine, twin screw extruder, multiple screw extruder or other form; The length-to-diameter ratio of forcing machine is in the 15-100 scope, and rotating speed is 10-500 rev/min, and controllable temperature can adopt a plurality of charging openings between 50-500 ℃, and additional side is to drawing-in device, liquid quantitative feeding device, vacuum pumping hardware.
4, the preparation method of partly cross-linked dystectic strength polypropylene according to claim 1 is characterized in that each section temperature that realizes the forcing machine in the process of the present invention is controlled at 50-250 ℃, and wherein the temperature of feed zone is lower than the temperature of other each section.
5, the preparation method of partly cross-linked dystectic strength polypropylene according to claim 1 is characterized in that described polypropylene is homopolymer polypropylene or multipolymer or its both blend.
6, the preparation method of partly cross-linked dystectic strength polypropylene according to claim 1, it is characterized in that described unsaturated silane is meant that all contain the silane of unsaturated group, comprise vinyltrimethoxy silane, vinyltriethoxysilane, vinyl ('beta '-methoxy oxyethyl group) silane, vinyl-triacetoxysilane, γ-propyl methacrylate base silane, vinyl trichloro silane, γ-[n-(β-isobutyl-acyl-oxygen ethyl)-n, n-alkyl dimethyl ammonium chloride] propyl trimethoxy silicane, styryl two aminopropyl silanes.
7, the preparation method of partly cross-linked dystectic strength polypropylene according to claim 1, it is characterized in that described alcoholysis agent is water and aquo compound or the compound that at high temperature can form water, comprise derivative, the calcium chloride of polyvinyl alcohol, beta-hydroxy acid and this alcohol acid of the aluminium hydroxide of being with crystal water, gypsum, short-chain branch; The compound of water generation reaction and composition at a certain temperature comprise the composition of organic acid and nonhygroscopic metal oxide, and organic acid comprises stearic acid, hexanodioic acid; Metal oxide comprises tin protoxide, zinc oxide.
8, the preparation method of partly cross-linked dystectic strength polypropylene according to claim 1, it is characterized in that described organic modified sheet silicate is meant the layered silicate of handling by ion-exchange etc. with organic intercalation agent, dispersion medium etc., or realize the layered silicate that organises with additive method; Wherein layered silicate is clay, carclazyte, polynite or Meccah stone, and organic intercalation agent comprises alkyl amine, the alkylammonium salt, and alcamines, several lactan, lauric acid amine, phenyl-ethyl amine, Ursol D, dispersion medium comprises water, alcohols, ketone.
9, the preparation method of partly cross-linked dystectic strength polypropylene according to claim 1, it is characterized in that described organic peroxide evocating agent comprises tertbutyl peroxide, 1,1,3,3,-tetramethyl--butylhydroperoxide, cumyl hydroperoxide, p-Methylisopropylbenzene base hydrogen peroxide, di-isopropylbenzene hydroperoxide, 2,5-dimethyl-2,5-two hydroperoxy hexanes, the cyclic group ketone peroxide, methyl cyclic group ketone peroxide, 3,3,5-trimethylammonium cyclic group ketone peroxide, ditertiary butyl peroxide, dicumyl peroxide, tert butyl isopropyl benzene peroxide, diacetyl peroxide, dipropyonyl peroxide, peroxidation two butyryl, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, two (3,5, the 5-trimethyl acetyl) superoxide, dibenzoyl peroxide.
10, the preparation method of partly cross-linked dystectic strength polypropylene according to claim 1, it is characterized in that described silicon alcohol condensation catalyst is an organometallic compound, comprise dibutyltin dilaurate, dibutyl tin two lauric acid salt, alkyl titanic acid ester, octene tin, lead octoate 36 or organic acid, lipid acid.
11, the preparation method of partly cross-linked dystectic strength polypropylene according to claim 1, it is characterized in that described grafting auxiliary agent refers to assistance and realizes silane and polyacrylic grafting, stop polypropylene molecular chain that the auxiliary agent of degraded takes place simultaneously, such grafting auxiliary agent comprises oxazoline, vinyl pyridine, Vinylstyrene, vinylbenzene.
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| CN100569818C (en) * | 2008-03-06 | 2009-12-16 | 中国科学院长春应用化学研究所 | A kind of method that improves melt strength of polypropylene |
| CN101284930B (en) * | 2007-04-12 | 2011-10-26 | 日立电线株式会社 | Method for preparing non-halogen fire retardant thermoplastic combinations |
| CN102603981A (en) * | 2012-02-29 | 2012-07-25 | 杨谢 | Formula and preparation method of silane grafted and crosslinked polypropylene (PP) |
| 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 |
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| CN101284930B (en) * | 2007-04-12 | 2011-10-26 | 日立电线株式会社 | Method for preparing non-halogen fire retardant thermoplastic combinations |
| CN100569818C (en) * | 2008-03-06 | 2009-12-16 | 中国科学院长春应用化学研究所 | A kind of method that improves melt strength of polypropylene |
| CN102603981A (en) * | 2012-02-29 | 2012-07-25 | 杨谢 | Formula and preparation method of silane grafted and crosslinked polypropylene (PP) |
| 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 |
| CN108570187B (en) * | 2018-05-08 | 2021-06-18 | 广州科莱瑞迪医疗器材股份有限公司 | Polypropylene plate for artificial limb orthopedic appliance and preparation method thereof |
| CN108570187A (en) * | 2018-05-08 | 2018-09-25 | 广州科莱瑞迪医疗器材股份有限公司 | A kind of prosthetic orthopedic apptss polypropylene board and preparation method thereof |
| CN114292364A (en) * | 2021-12-21 | 2022-04-08 | 日丰企业集团有限公司 | Silane grafted polypropylene, crosslinked polypropylene material and preparation method thereof |
| CN114292364B (en) * | 2021-12-21 | 2022-12-02 | 日丰企业集团有限公司 | Silane grafted polypropylene, crosslinked polypropylene material and preparation method thereof |
| CN115403863A (en) * | 2022-09-30 | 2022-11-29 | 金发科技股份有限公司 | Polypropylene composition and preparation method and application thereof |
| CN115403863B (en) * | 2022-09-30 | 2023-12-15 | 金发科技股份有限公司 | Polypropylene composition and preparation method and application thereof |
| CN116036154A (en) * | 2023-01-13 | 2023-05-02 | 青岛大学 | Water supplementing, mite removing and bacteria inhibiting hydrogel eye mask and preparation method and application thereof |
| CN116003912A (en) * | 2023-02-10 | 2023-04-25 | 创合新材料科技江苏有限公司 | Special polypropylene reinforcing material for micro-crosslinked high-pressure-resistant water pump and preparation method and application thereof |
| CN116003912B (en) * | 2023-02-10 | 2024-01-09 | 创合新材料科技江苏有限公司 | Special polypropylene reinforcing material for micro-crosslinked high-pressure-resistant water pump and preparation method and application thereof |
| CN117946527A (en) * | 2024-03-22 | 2024-04-30 | 成都力多美科技有限公司 | Semi-solidified solid self-solidified silicon rubber sheet and preparation method thereof |
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