CN102757565B - Preparation method of long chain branched polyethylene - Google Patents
Preparation method of long chain branched polyethylene Download PDFInfo
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Abstract
The invention discloses a preparation method of long chain branched polyethylene. The preparation method comprises the following steps of: A, under the action of an initiator, performing a graft reaction on a vinyl monomer containing a polyfunctional group, and a polyethylene substrate under the synergistic action of a second olefin monomer to obtain grafted polyethylene of which the side chain is provided with a functional group; B, and performing a branching reaction on the grafted polyethylene obtained in the step A and an additive to obtain long chain branched polyethylene in which the additive is taken as a core and a polyethylene macromolecule is taken as an arm. Due to the adoption of the preparation method disclosed by the invention, long chain branched polyethylene with high melt strength can be produced, the branching degree is relatively controllable, the cost is low, the production efficiency is high, and superior foaming performance is realized. Expanded polyethylene with various functionality such as a wood-plastic composite expanded material added with wood fiber, an enhanced polyethylene expanded material added with glass fiber, a fire-proof polyethylene expanded material added with an expansion flame retardant and the like can be prepared according to different use requirements.
Description
Technical field
The present invention relates to Organic chemical products, relate in particular to the poly preparation method of a kind of drawing money on credit.
Background technology
Polyvinyl resin is one of thermoplastic macromolecule material being most widely used.Matter is soft owing to having for the polyethylene foam-material being obtained by foaming technique by polyvinyl resin, good toughness, elastic recovery are good, nontoxic etc., and feature is widely used.But in the kind of polyvinyl resin, only have Low Density Polyethylene and linear low density polyethylene to be directly used for foaming, and high density polyethylene(HDPE) is owing to there is no branched structure, melt strength is lower cannot be used for carrying out foaming.Yet, on the other hand, although Low Density Polyethylene and linear low density polyethylene have reasonable foam performance, yet because their melt flow rate (MFR) is too high, when carrying out the machine-shaping of the foamed board of thickness over 20 centimetres, foam was subject to the effect of gravity that transverse flow can occur before solidifying, and caused foamed board became uneven even, thereby impact is used.In addition, due to Low Density Polyethylene and linear low density polyethylene resin itself softer, therefore the polyethylene making is also softer, while using as cushioning material, be subject to certain restrictions, and to expect the polyethylene that hardness is higher, best bet is to use high density polyethylene(HDPE) to foam.The present invention is exactly some inherent defects during for polyethylene itself and foaming, pass through chemical reaction, polyethylene and filler particle are connected with the form of chemical bond, thereby form, take the organic or inorganic thing of dosing as core, the drawing money on credit polyethylene structure that the polyethylene macromole of take is arm.Not only greatly improve by this method poly melt strength, and improved the dispersive ability of weighting material in polyethylene matrix, can play the effect of enhanced polyethylene mechanical property.In addition, when carrying out polyethylene foam, this homodisperse weighting material plays the effect of nucleator on the one hand, promote the formation of more abscesses, on the other hand, these weighting materials can be accelerated the crystallisation by cooling speed after polyethylene foam, thereby improve the curing speed of foam polyethylene.Therefore, by method of the present invention, can effectively improve poly foam performance.
At present PE modified method is adopted the method for polyethylene and other resin alloy more, or adopt the method for peroxide crosslinking, cross-linking radiation and crosslinked with silicane, improve the melt strength of foamed substrate.If patent CN1204355 is using a kind of hybrid resin of Low Density Polyethylene, a kind of linear low density polyethylene and a kind of linear high-density polyethylene of producing by high-pressure process as foaming matrix, made noncrosslinking polyvinyl resin bead, this pre-frothing bead can be used for the formed body that in-molded production has complicated shape.In addition, patent CN 101679659 also discloses a kind of foam polyethylene, the blend that it contains 95.5wt%-99.5wt% Low Density Polyethylene and 0.5wt%-4.5wt% high density polyethylene(HDPE).This polyethylene foam matrix can be prepared the foams that do not contain ripple, and has improved optical signature, improved heat insulating ability and improved mechanical property.Yet by the method for this simple blend, be difficult to increase substantially the melt strength of resin matrix, so just easily cause foaming unstable, bubble easily breaks, and is difficult to improve the degree of stability of foaming process.Patent CN 102030910A and patent CN 1343739 utilize the method for irradiation to prepare the polyethylene that can foam; Patent CN 1534061 and CN 1369520 utilize the method for peroxide crosslinking to prepare a kind of crosslinked polyethylene elastomer foam materials, and the foam of preparation has outstanding tearing toughness and rebound resilience in this way; Patent CN101134826 utilizes the method for crosslinked with silicane to prepare a kind of crosslinked polythene material, and utilizing this material to manufacture can resistant to elevated temperatures polyethylene foam product material.Yet on the whole, the method for irradiation is subject to thickness limits, there is the shortcomings such as cost is high, source of radiation is limited; Peroxide crosslinking method exists cladodification rate low, and easily degraded or excessively crosslinked, the defect such as is difficult to stablize; And silane cross-linking method exists and need use water as linking agent, complete after goods crosslinkedly again, in fact except making tubing, lack other industrial production and be worth.There is different defects in visible above several conventional methods, can not meet poly long shootization and industrial applications.
Of the present inventionly take the organic or inorganic thing of dosing as core, the drawing money on credit preparation method for polythene that the polyethylene macromole of take is arm has overcome the shortcoming of above method, and poly long shootization and the promotion of foaming technique are had great importance.
In polycthylene grafted step of the present invention, feature of the present invention is, can control containing the multi-functional vinyl monomer grafting content in sub polyethylene subchain and effectively prevent the degraded of polycthylene grafted product and crosslinked; Another one feature of the present invention is, by adding inorganic or organic method of dosing thing, not only can make sub polyethylene subchain and dose thing to be coupled to each other with covalent linkage, formation be take and dosed thing as core, the long branched structure of polyethylene that the polyethylene macromolecular chain of take is arm, and be evenly distributed on dosing thing can also play the effect of nucleator in the process of foaming in polyethylene matrix.Therefore, method of the present invention contributes to greatly to improve poly foam performance.
Summary of the invention
Object of the present invention, exactly in order to provide a kind of drawing money on credit poly preparation method, greatly to improve poly foam performance.
In order to achieve the above object, the present invention has adopted following technical scheme: the poly preparation method of a kind of drawing money on credit, comprises the following steps:
A, prepare grafted polyethylene
Under the effect of initiator, make to contain multi-functional vinyl monomer and carry out graft reaction with polyethylene matrix under the synergy of the second olefinic monomer, prepare side chain with the grafted polyethylene of functional group;
B, the long branched polyethylene of preparation
By steps A gained grafted polyethylene with dose thing and carry out branching reaction, or by steps A gained grafted polyethylene with dose thing and in the presence of oxidation inhibitor, carry out branching reaction, the long branched polyethylene that to prepare to dose thing be core, the polyethylene macromole of take is arm.
Raw material and weight part proportioning related in steps A are as follows:
100 parts of polyethylene matrixes;
Contain 0.1～25 part of multi-functional vinyl monomer;
The second 1～25 part of olefinic monomer;
0.02～10.0 part of initiator;
Raw material and weight part proportioning related in step B are as follows:
100 parts of grafted polyethylenes;
Dose 0.1～50 part of thing;
0～10 part, oxidation inhibitor.
Graft reaction described in steps A adopts solution graft copolymerization reaction or melting graft reaction;
Solution graft copolymerization reaction is: the various materials except initiator are joined in dimethylbenzene, toluene, trichlorobenzene or chloroform, progressively heat up, and stir, the homogeneous solution that formation polymerized ethylene content is 5%-15%, drum nitrogen is got rid of after oxygen, divide and progressively add initiator 3-5 time, holding temperature reaction 2-4 hour, after reaction finishes, lowers the temperature reaction soln, solid is separated out, after filtration, obtain grafted polyethylene after dry;
In solution graft copolymerization reaction, if temperature of reaction lower than 100 ℃, polyethylene may dissolve not exclusively, makes graft reaction be difficult to carry out.If temperature of reaction is too high, the violent boiling of solvent can not stablize graft reaction to carry out.
Melting graft reaction is: after various materials are fully mixed in high-speed mixer, join in Haake, single screw extrusion machine, twin screw extruder, Banbury mixer, banbury mixers or mill, at 100 ℃-250 ℃, carry out melting graft reaction, reaction times is 1min-30min, product is cooling, pelletizing, make grafted polyethylene.
In melting graft reaction, if temperature of reaction lower than 100 ℃, polyethylene melting completely, graft reaction is difficult to carry out.If temperature of reaction higher than 250 ℃, not only can reduce poly percentage of grafting, also can make polyolefin product degraded, worsen its physicals.If the reaction times is less than 1min, graft reaction can not carry out completely, affects poly percentage of grafting, and residual initiator also can worsen the performance of polyethylene product.If the reaction times is greater than 30min, likely make polyethylene degraded.
Branching reaction described in step B adopts solution branching reaction or melting branching reaction;
Solution branching reaction is: the graft polyolefin of preparation and oxidation inhibitor are joined in dimethylbenzene, toluene, trichlorobenzene or chloroform, progressively heat up, and stir, forming the uniform liquid of 5%-15%, drum nitrogen is got rid of after oxygen, the disposable weighting material that adds, holding temperature reaction 0.1～1 hour, after reaction finishes, lowers the temperature reaction soln, solid is separated out, after filtration, obtain long branched polyethylene after dry.
Melting branching reaction is: grafted polyethylene, oxidation inhibitor and weighting material is even in high-speed mixer and mixing, then join in Haake, single screw extrusion machine, twin screw extruder, Banbury mixer, banbury mixers or mill, at 130 ℃-250 ℃, carry out frit reaction, reaction times is 1min-30min, product is cooling, pelletizing, make long branched polyethylene.
Described polyethylene matrix is selected from one or more in high density polyethylene(HDPE), Low Density Polyethylene, linear low density polyethylene, and its melt flow rate (MFR) is between 0.1g/10min～50g/10min.Preferred melt flow rate (MFR) is 1g/10min～30g/10min, and further preferred melt flow rate (MFR) is 1g/10min～20g/10min.Melt flow rate (MFR) is too large or too little, is all unfavorable for polyvinyl resin and contains reacting of multi-functional vinyl monomer, thereby reducing reaction efficiency, affects final grafted polyethylene and the organic or inorganic reaction effect of dosing thing.The present invention does not do concrete restriction to used poly kind, main according to wherein one or several of the purposes choice for use of the polyethylene foam-material that will prepare, combines use.
Described is selected from one or more in vinylformic acid, maleic anhydride, methacrylic acid, fumaric acid, methylene-succinic acid, undecylenic acid, glycidyl methacrylate, acrylamide, N hydroxymethyl acrylamide, Hydroxyethyl acrylate, Propylene glycol monoacrylate containing multi-functional vinyl monomer.From with dose thing surface functional group reactive behavior angle, preferably vinylformic acid, methacrylic acid, glycidyl methacrylate and maleic anhydride, further preferable methyl glycidyl acrylate and maleic anhydride monomer, most preferably maleic anhydride monomer.The addition of vinyl monomer is preferably 2～18 parts, more preferably 3～12 parts.If the consumption of grafted monomer is greater than 25 parts, can make to produce more homopolymer between grafted monomer, affect the mechanical property of polyethylene matrix; But if the addition of polyfunctional monomer is less than 0.1 part, be difficult to reach and the object of dosing thing surface group and reacting.
The second described olefinic monomer is selected from one or more in vinylbenzene, Vinylstyrene, alpha-methyl styrene, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate.Addition is preferably 1～18 part, more preferably 2～12 parts.Add olefinic monomer can improve the reaction efficiency containing multi-functional vinyl monomer on the one hand, can suppress poly degraded on the other hand.If but the consumption of olefinic monomer is greater than 25 parts, can make the second olefinic monomer produce more homopolymer, affect the performance of polyethylene foam matrix.
Described initiator is selected from one or several in dicumyl peroxide, benzoyl peroxide, dilauroyl peroxide, ditertiary butyl peroxide, tertbutyl peroxide, tert butyl peroxy benzoate, Isosorbide-5-Nitrae-bis-(tert-butyl hydroperoxide sec.-propyl) benzene, azobisisobutyronitrile, azo two eyeball in different heptan.Its addition is preferably 0.1～5 weight part, more preferably 0.5～3 weight part.If the consumption of initiator is lower than 0.1 part (weight part), the number of free radical of generation is too low, can reduce polyfunctional group vinyl monomer and poly reaction efficiency, affects the use properties of polyethylene matrix.But if the consumption of initiator is greater than 10.0 parts (weight parts), can cause the crosslinked and DeR that polyethylene is serious, in addition, remaining initiator also can worsen the performance of polyethylene foamed matrix.
Described weighting material is selected from one or several in sawdust, wood fibre, starch, oyster shell whiting, glass fibre, calcium carbonate, talcum powder, silicon-dioxide, polynite, molecular sieve, titanium dioxide, kaolin, glass microballon, carbon black, zinc oxide, magnesium oxide, aluminum oxide, zinc hydroxide, magnesium hydroxide, aluminium hydroxide, and its particle size is less than 100 microns.For organic weighting material, preferably use sawdust, wood fibre and each kind of starch, further preferably use wood powder and wood fibre; Its addition is preferably 1～50 weight part, and more preferably 1～30 weight part, most preferably is 1～20 weight part; Its size is not done concrete restriction, as long as matrix mechanical property is not significantly affected after joining in polyethylene.For inorganic filler, preferably use calcium carbonate, talcum powder, silicon-dioxide, carbon black, zinc oxide, magnesium oxide, aluminum oxide, zinc hydroxide, magnesium hydroxide, aluminium hydroxide, further preferably use calcium carbonate, talcum powder, zinc oxide, aluminum oxide, most preferably use calcium carbonate and talcum powder; Its addition is preferably 1～50 weight part, and more preferably 1～30 weight part, most preferably is 1～20 weight part; Its particle size is preferably less than 100 microns.
Described oxidation inhibitor is selected from 2,6-di-t-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-methy phenol, 2,6-di-t-butyl-alpha, alpha-dimethyl amino-p-cresol, 2, one or more in 4,6-tri-butyl-phenol, Tyox B, thio-2 acid two (octadecyl ester), thio-2 acid two (14 ester), antioxidant 1010, antioxidant CA, oxidation inhibitor B215, oxidation inhibitor B225.Oxidation inhibitor add response situation and the fluidity of molten that can regulate grafted polyethylene and dose thing, if but add-on is greater than 10 parts, can worsen the use properties of polyethylene foam matrix.
The thing of dosing that adopts the poly preparation method of drawing money on credit of the present invention can produce to be evenly distributed in polyethylene matrix is core, take polyethylene macromolecular chain as arm, the long shootization polyethylene with high fondant-strength, its degree of branching is relatively controlled, with low cost, productivity is high, and has outstanding foam performance.Can prepare various functional polyethylene foameds according to different service requirementss, for example be added with the Wood-plastic-foamed composite of wood fibre, be added with the enhancement polyethylene foam-material of glass fibre, and be added with fire line polyethylene foam-material of expansion type flame retardant etc.
Embodiment
One, grafted polyethylene is containing the mensuration of polyfunctional group vinyl monomer percentage of grafting
Adopt the resulting grafted polyethylene of examination of infrared spectrum containing polyfunctional group vinyl monomer percentage of grafting, measure the relative intensity of characteristic peak before and after its extraction, according to langbobier law, can obtain reaction efficiency.Calculation formula is:
Reaction efficiency=100%*C
2/ (1-C
1)
Wherein, C
1---the concentration of polyfunctional group grafted monomer in proportioning;
C
2---the concentration of polyfunctional group grafted monomer after extracting
1-C
1---poly concentration before extracting, is poly initial charge.
Two, the mensuration of drawing money on credit Melt Flow Rate of Polyethylene (MFR)
MFR, measures under 2.16kg load at 190 ℃ with SRSY-1 melt flow rate (MFR) determinator.
Three, the mensuration of drawing money on credit polyethylene melt intensity
Being determined on Gottfert Rheotens melt strength tester of polyethylene specimen melt strength carried out.Melt strength tester, with the roller of a secondary incorgruous rotation, can draw polyethylene melt in vertical direction with 20mm/s during test
2acceleration carry out accelerated motion.Probe temperature is 180 ℃, and during melt fracture, the measured power of tester is poly melt strength.
Four, the mensuration of drawing money on credit polyethylene foam performance
Poly foaming is 35mm at screw diameter, on the twin screw extruder that length-to-diameter ratio is 48: 1, carries out, and blowing temperature is set in 150 ℃, and the rotating speed of forcing machine is 80rpm, and whipping agent used is supercritical CO
2, the consumption of whipping agent is 30% of polypropylene weight.
Below by several embodiment, to of the present invention, further illustrate
The poly preparation of embodiment 1 drawing money on credit in solution:
Get 100 grams of polyethylene 2200J (Daqing petrochemical, melting index 6.0g/10min), join in the flask of 2000ml, then add 1300 grams of dimethylbenzene, be progressively warming up to 130 ℃.After solid all dissolves, add 2 grams, vinylformic acid, 2 grams of vinylbenzene then divided 0.36 gram of benzoyl peroxide to join in flask for 5 times in 30 minutes, maintained 130 ℃ of reactions.After reaction finishes, flask is cooled to room temperature, adds 100 grams of acetone, through stirring after solid is separated out completely, be placed in vacuum drying oven and be dried, obtain grafted polyethylene.Vinylformic acid and poly percentage of grafting the results are shown in Table 1.
Get in the flask that 0.24 gram, grafted polyethylene that 49g prepared by aforesaid method and 1010 oxidation inhibitor join 2000ml, then add 1000 grams of dimethylbenzene, be progressively warming up to 130 ℃.After solid all dissolves, by 1g particle diameter, being that 400 object calcium carbonate are disposable joins in flask, maintains 130 ℃ of reactions.After reaction finishes, flask is cooled to room temperature, adds 100 grams of acetone, through stirring after solid is separated out completely, be placed in vacuum drying oven and be dried, obtain long shootization polyethylene.The poly properties of long shootization is listed in table 1.
Reference examples 1: the grafted polyethylene of getting 49g embodiment 1 preparation.Polyethylene, with to dose the method that thing reacts identical with embodiment 1, just dosed thing and is changed 1g silicon-dioxide into by calcium carbonate, and the poly properties of the long shootization obtaining is listed in table 1.
The poly preparation of embodiment 2 drawing money on credit of use scorification:
Get polyethylene 2200J (Daqing petrochemical, melting index 6.0g/10min) 10 kilograms, 0.2 kilogram of glycidyl methacrylate graft monomer, 0.2 kilogram of vinylbenzene, 36 grams of dicumyl peroxides, dicumyl peroxide is dissolved in glycidyl methacrylate and cinnamic monomer, then all puts into high-speed mixer and mix 2 minutes, discharging.Compound is joined in the twin screw extruder that is preheating to 170 ℃, with the tachyphylaxis of 50rpm, extrude.Extrude product and after pelletizing, obtain grafted polyethylene.Glycidyl methacrylate and poly percentage of grafting the results are shown in Table 1.
Get 4.9 kilograms of grafted polyethylenes of preparing by aforesaid method, 20 grams, oxidation inhibitor, 20 grams of catalyzer, 100 grams, pine sawdust, then all puts into high-speed mixer and mixes 2 minutes, discharging.Compound is joined in the twin screw extruder that is preheating to 180 ℃, with the tachyphylaxis of 80rpm, extrude.Extrude product and after pelletizing, obtain long branched polyethylene.The poly properties of long shootization is listed in table 1.
Reference examples 2: the grafted polyethylene of getting 4.9 kilograms of embodiment, 2 preparations.Grafted polyethylene is identical with embodiment 2 with the reaction method of dosing thing, just 100 gram of 400 object talcum powder is joined in grafted polyethylene and is reacted as dosing thing.The poly properties of long shootization obtaining is listed in table 1.
Embodiment 3: grafting method is identical with embodiment 2, just using maleic anhydride as grafted monomer and polyethylene carry out graft reaction.It is with to dose the method that thing pine sawdust reacts also identical with embodiment 2.Maleic anhydride and poly percentage of grafting result and the poly properties of long shootization obtaining are listed in table 1.
Reference examples 3: the grafted polyethylene of getting 4.9 kilograms of embodiment, 3 preparations.Grafted polyethylene is with to dose the method that thing reacts identical with embodiment 3, just 100 gram of 400 object talcum powder joined in grafted polyethylene and reacted as dosing thing.The poly properties of long shootization obtaining is listed in table 1.
Table 1
As can be seen from Table 1, vinylformic acid, glycidyl methacrylate and maleic anhydride can with polyethylene generation graft reaction, and percentage of grafting is all higher, and the percentage of grafting of vinylformic acid and glycidyl methacrylate is higher, this may be that the consistency of both and polyvinyl resin matrix is better, and maleic anhydride is because homopolymerization can not occur for self, therefore with poly grafting efficiency than both are lower above.
From table 1, it can also be seen that, can there is chemical reaction with the surface of calcium carbonate in polycthylene grafted acryhic, generated branched structure, and melt strength is improved.Yet because vinylformic acid can not react with silicon-dioxide, therefore, in reference examples 1, the melt flow rate (MFR) of sample is compared with polyethylene raw material with melt strength does not have too large variation substantially.In embodiment 2 and reference examples 2, epoxide group on polyethylene to graft glycidyl methacrylate macromole can carry out chemical reaction with the hydroxyl of dosing thing surface, therefore, the long branched polyethylene obtaining has reasonable foam performance, but because the activity of epoxide group is not high, so its melt strength is not still greatly enhanced.In embodiment 3 and reference examples 3, anhydride group on Research of Grafting Malaic Anhydride Onto Polyethylene macromole has very high activity, can carry out chemical reaction with the multiple lip-deep hydroxyl of thing of dosing at an easy rate, generation be take and dosed thing as core, the branched structure that the polyethylene macromole of take is arm, is greatly enhanced the melt strength of product and foam performance.In addition, in embodiment 3, there is more hydroxyl on the surface of dosing thing due to pine sawdust, and the product therefore obtaining has the highest melt strength and best foam performance.
Claims (5)
1. the poly preparation method of drawing money on credit, is characterized in that, comprises the following steps:
A, prepare grafted polyethylene
Under the effect of initiator, make to contain multi-functional vinyl monomer and carry out graft reaction with polyethylene matrix under the synergy of the second olefinic monomer, prepare side chain with the grafted polyethylene of functional group;
B, the long branched polyethylene of preparation
By steps A gained grafted polyethylene with dose thing and carry out branching reaction, or by steps A gained grafted polyethylene with dose thing and in the presence of oxidation inhibitor, carry out branching reaction, the long branched polyethylene that to prepare to dose thing be core, the polyethylene macromole of take is arm;
Raw material and weight part proportioning related in steps A are as follows:
Raw material and weight part proportioning related in step B are as follows:
100 parts of grafted polyethylenes;
Dose 0.1～50 part of thing;
0～10 part, oxidation inhibitor;
Graft reaction described in steps A adopts solution graft copolymerization reaction or melting graft reaction;
Solution graft copolymerization reaction is: the various materials except initiator are joined in dimethylbenzene, toluene, trichlorobenzene or chloroform, progressively heat up, and stir, the homogeneous solution that formation polymerized ethylene content is 5%-15%, drum nitrogen is got rid of after oxygen, divide and progressively add initiator 3-5 time, holding temperature reaction 2-4 hour, after reaction finishes, lowers the temperature reaction soln, solid is separated out, after filtration, obtain grafted polyethylene after dry;
Melting graft reaction is: after various materials are fully mixed in high-speed mixer, join in single screw extrusion machine, twin screw extruder, Banbury mixer, banbury mixers or mill, in 100-℃ 250 times ℃, carry out melting graft reaction, reaction times is 1min-30min, product is cooling, pelletizing, make grafted polyethylene;
Branching reaction described in step B adopts solution branching reaction or melting branching reaction;
Solution branching reaction is: the graft polyolefin of preparation and oxidation inhibitor are joined in dimethylbenzene, toluene, trichlorobenzene or chloroform, progressively heat up, and stir, forming the uniform liquid of 5%-15%, drum nitrogen is got rid of after oxygen, dose thing disposable adding, holding temperature reaction 0.1～1 hour, after reaction finishes, lowers the temperature reaction soln, solid is separated out, after filtration, obtain long branched polyethylene after dry;
Melting branching reaction is: by grafted polyethylene, oxidation inhibitor with to dose thing even in high-speed mixer and mixing, then join in single screw extrusion machine, twin screw extruder, Banbury mixer, banbury mixers or mill, at 130-℃ 250 ℃, carry out frit reaction, reaction times is 1min-30min, product is cooling, pelletizing, make long branched polyethylene;
Described is selected from one or more in vinylformic acid, maleic anhydride, methacrylic acid, fumaric acid, methylene-succinic acid, undecylenic acid, glycidyl methacrylate, acrylamide, N hydroxymethyl acrylamide, Hydroxyethyl acrylate, Propylene glycol monoacrylate containing multi-functional vinyl monomer;
The described thing of dosing is selected from one or several in sawdust, wood fibre, starch, oyster shell whiting, glass fibre, calcium carbonate, talcum powder, silicon-dioxide, polynite, molecular sieve, titanium dioxide, kaolin, glass microballon, carbon black, zinc oxide, magnesium oxide, aluminum oxide, zinc hydroxide, magnesium hydroxide, aluminium hydroxide, and its particle size is less than 100 microns.
2. the poly preparation method of drawing money on credit according to claim 1, it is characterized in that: described polyethylene matrix is selected from one or more in high density polyethylene(HDPE), Low Density Polyethylene, linear low density polyethylene, and its melt flow rate (MFR) is between 0.1g/10min～50g/10min.
3. the poly preparation method of drawing money on credit according to claim 1, is characterized in that: the second described olefinic monomer is selected from one or more in vinylbenzene, Vinylstyrene, alpha-methyl styrene, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate.
4. the poly preparation method of drawing money on credit according to claim 1, it is characterized in that: described initiator is selected from one or several in dicumyl peroxide, benzoyl peroxide, dilauroyl peroxide, ditertiary butyl peroxide, tertbutyl peroxide, tert butyl peroxy benzoate, Isosorbide-5-Nitrae-bis-(tert-butyl hydroperoxide sec.-propyl) benzene, azobisisobutyronitrile, azo two eyeball in different heptan.
5. the poly preparation method of drawing money on credit according to claim 1, it is characterized in that: described oxidation inhibitor is selected from 2,6-di-t-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-methy phenol, 2,6-di-t-butyl-alpha, alpha-dimethyl amino-p-cresol, 2, one or more in 4,6-tri-butyl-phenol, Tyox B, thio-2 acid two (octadecyl ester), thio-2 acid two (14 ester), antioxidant 1010, antioxidant CA, oxidation inhibitor B215, oxidation inhibitor B225.
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