CN1183175C - New type polyolefin functionality special-purpose material - Google Patents
New type polyolefin functionality special-purpose material Download PDFInfo
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Abstract
The present invention discloses a novel polyolefin functionality special material. The functionality special material is prepared from a specific amount of polyolefine resin, specific formed polyhydroxypolyether, a specific amount of styrene, a specific number of initiators and a specific number of antioxidants by a solution grafting, solid phase grafting or melting grafting method. The functionality special material and the corresponding polyolefine resin are blended to obtain a resin composition with good and balanced performance at aspects of coating decoration performance, processing performance, antistatic performance, rigidity, hardness, shock resistance, etc.
Description
The invention belongs to high molecular polymer polymerization and processing technique field, relate to a kind of functionality special-purpose material that adopts multi-hydroxy polyether as the polyolefin resines such as polyethylene, polypropylene and ethylene-propylene copolymer of graft modification polar monomer.
For many years, because polyolefin resines such as polyethylene, polypropylene and ethylene-propylene copolymer have good performance, as: density is little, raw material sources are abundant, low price, water-fast, oil resistant and resistance to chemical attack, non-environmental-pollution etc., makes them be widely used in every field.But because polyolefinic high-crystallinity and low polarity cause their surface daub on a wall poor, and has very strong static easily, their application is subjected to restriction to a certain degree thus.
For improving the surface daub on a wall of polyolefin resin, all be to adopt the method for introducing polar functional group on the surface of polyolefin resin usually, as:
(1) surface preparation: comprise flame method, corona discharge method, aciding, oxide treatment method, plasma processing method etc., this method is carried out secondary treatment to polyolefin articles, and technology is loaded down with trivial details, the cost height;
(2) surface-coated method: base coating is coated in polyolefinic surface, and method is easy, but still there is very big problem in the tack between base coating and the polyolefine;
(3) base material modification method: comprising copolymerization method and grafting method, is the main method that adopts in recent years.Wherein grafting method has solution grafting, solid phase grafting method and fusion-grafting method.From environmental protection and the convenient angle of technology, the fusion-grafting method is a kind of grafting method that is used at most.
Among patent EP429236, US4888391, JP05/117574 and the JP05/179080, adopt the ester compound of olefines material and unsaturated acid or unsaturated acid to carry out copolyreaction, acquisition contains the multipolymer of polar group, add to then in the polyolefin resin, improve the surface daub on a wall of resin.Compare with copolymerization method, the fusion-grafting method is more easy, easily realizes.The fusion-grafting method is to carry out graft reaction when melt blending, makes on the molecular polyolefin chain and introduces polar group, and it can be realized in general mixing equipment.Patent JP05/295226, JP05/295227, JP07/118488, EP567058, JP04/63817 adopt unsaturated carboxylic acid or acid anhydrides and polyolefine to carry out graft reaction, reach the purpose of improving the polyolefin resin paintability.But,, exist percentage of grafting acidic-group low and that introduce to cause the disadvantages such as degraded of polyolefin substrate easily with unsaturated carboxylic acid or acid anhydrides and polyolefine grafting.Patent JP05/11758, JP07/118487, JP04/07112, EP684281, the method that the olefin oligomer of employing interpolation hydroxyl carries out modification to polyolefine, but, improve limited to polar because the hydroxy radical content of additive is less.In addition, in order to allow these short hydroxyls can move to polyolefinic surface, the molecular weight of graft polyolefin just can not be high, and this is unfavorable for the shock resistance of material again.Therefore, this class modification method can not satisfy the isostatic requirement of paintability and mechanical property simultaneously.
The objective of the invention is to improve the defective of above-mentioned technology, disclose a kind of employing multi-hydroxy polyether as the monomeric new type polyolefin resin of grafting-modified polar functionality special-purpose material.
Because multi-hydroxy polyether has more hydroxyl, guaranteed that can be polyolefine under the situation of same percentage of grafting provides better polarity.In addition, because the surfactivity effect of polyethers and high wetting ability and polarity, make it be easy to be distributed to polyolefinic surface, and do not rely on the reduction of graft polyolefin molecular weight, thereby can not reduce the shock resistance of material because of the lower molecular weight of graft polyolefin.On the contrary, because the special interface shock absorption that graft polyether produced, can improve the shock resistance of material widely.
With functionality special-purpose material of the present invention and corresponding polyolefin resin blend, can obtain that various aspects of performance such as paintability, processibility, static resistance, rigidity, hardness and shock resistance are good, the isostatic resin combination.
Said functionality special-purpose material is by the polyolefin resin of specified quantitative, the multi-hydroxy polyether of specific composition, and the vinylbenzene of specified quantitative, the initiator of specified quantitative and the oxidation inhibitor of specified quantitative, the method by solution graft copolymerization, solid phase grafting or fusion-grafting obtains.
The raw material that functionality special-purpose material adopted and the consumption that prepare said polyolefin resin are as described below:
The polyolefin resin of (1) 60%～95% (weight), this resin are polyvinyl resin, acrylic resin or ethylene-propylene copolymer, and melt flow rate (MFR) is 4～40g/10min;
The multi-hydroxy polyether of (2) 5%～40% (weight), their hydroxyl value scope should contain 1～3 activity double key 100～700, and feature structure is as follows:
Wherein: n=4～20, R
1Be the polyvalent alcohol end group, comprise: propylene glycol, ethylene glycol, glycerol, pentanediol, hexylene glycol, tetramethylolmethane, TriMethylolPropane(TMP) and butantetraol; R
2For-H or-CH
3, R
3For containing active unsaturated double-bond compound, as vinylformic acid, acrylate, methacrylic ester, maleic acid ester, fumarate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate etc.;
The vinylbenzene of (3) 1.0%～5.0% (weight);
The initiator of (4) 0.2%～5.0% (weight);
The oxidation inhibitor of (5) 0.02%～1.0% (weight);
Weight percent is a benchmark with the total amount of component (1)～(2) all.
Said polyolefin resin is polyvinyl resin, acrylic resin or ethylene-propylene copolymer, and melt flow rate (MFR) is 4～40g/10min.If the melt flow rate (MFR) of polymkeric substance is less than 4g/10min, and then the functionality special-purpose material of gained is not only mobile poor, and is unfavorable for that the surface that hydroxyl is diffused into the polyolefin resin goods comes up.But greater than 40g/10min, then the functionality special-purpose material of gained will influence the mechanical property of polyolefin resin, particularly shock resistance as if the melt melting rate.Therefore, the melt flow rate (MFR) of polymkeric substance is comparatively suitable within 4～40g/10min scope.
The hydroxyl value scope of said multi-hydroxy polyether is 100～700.If the hydroxyl value of multi-hydroxy polyether has two kinds of situations so less than 100, and the one, the hydroxyl value of polyethers initiator is very few, and the 2nd, the molecular weight of polyethers is excessive.The former makes the improvement ability drop of functionality special-purpose material to polyolefin surfaces polarity and paintability; The latter can make the processing fluidity of functionality special-purpose material descend again.Yet greater than 700, promptly the molecular weight of polyethers is too small as if hydroxyl value, and the ability that the one side hydroxyl is diffused into the surface descends to some extent, is unfavorable for improving the shock resistance of material on the other hand.Therefore, the OK range of multi-hydroxy polyether hydroxyl value is 100～700; Its consumption is 5.0%～40% (weight).If the consumption of multi-hydroxy polyether is less than 5.0% (weight), then the polar group amount of gained functionality special-purpose material reduces, and can not reach the purpose of improving the polyolefin resin paintability.And if the consumption of multi-hydroxy polyether on the one hand, can cause the crosslinked of polyolefin resin greater than 40% (weight), reduces the mobile and dispersiveness in matrix of functionality special-purpose material; On the other hand, can cause in a large number not that the grafted multi-hydroxy polyether remains in the polyolefin resin matrix, become objectionable impurities.Moreover the consumption that improves multi-hydroxy polyether also can increase the cost of polyolefin functionality special-purpose material.
Said cinnamic consumption is 1.0%～5.0% (weight).Cinnamic consumption does not then have the effect that improves the multi-hydroxy polyether percentage of grafting if be lower than 1.0% (weight).But, reduce the mechanical property of material if cinnamic consumption greater than 5.0% (weight), can produce the vinylbenzene homopolymerization.
The consumption of said initiator is 0.2%～5.0% (weight).If the consumption of initiator is lower than 0.2% (weight), the number of free radical of generation is too low, and the multi-hydroxy polyether percentage of grafting will reduce greatly, influences the paintability of polyolefin functionality special-purpose material.In addition, remaining polyethers can become objectionable impurities, makes the mis-behave of material.If the consumption of initiator is greater than 5.0% (weight), then the termination reaction between polyolefine macromolecular radical and the initiator free radical is accelerated, and makes percentage of grafting descend; Cause the degraded of polyolefin substrate molecular chain and the generation of crosslinking reaction simultaneously, paintability, mechanical property and the flowability of functionality special-purpose material are descended simultaneously.
Said initiator can comprise dicumyl peroxide, benzoyl peroxide, dilauroyl peroxide, ditertiary butyl peroxide, tertbutyl peroxide, tert butyl peroxy benzoate etc.Can use one or more initiators wherein to unite use separately.
The consumption of said oxidation inhibitor is 0.02%～1.0% (weight).Consumption then can not play the effect that prevents the polyolefin resin degraded less than 0.02% (weight).If consumption is greater than 1.0% (weight), number of free radical reduces in the time of can making graft reaction again, can not produce effective grafting.
Said oxidation inhibitor comprises 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, 2,4,6-tri-butyl-phenol, Tyox B, thio-2 acid two (octadecyl ester), thio-2 acid two (14 ester), antioxidant 1010, antioxidant CA etc.Can use one or more oxidation inhibitor wherein to unite use separately.
In order to make prepared PP Pipe Compound that satisfactory stability and processibility be arranged, in batching, can add an amount of additive, said additive is one or more in UV stabilizer, lubricant or the pigment.
Said UV stabilizer comprises Octabenzone, 2-hydroxyl-4-octadecane oxygen base benzophenone, 2-hydroxyl-4-dodecyloxy benzophenone etc.; Said lubricant comprises mustard acid amides, N, N '-ethylene bis stearamide, amine hydroxybenzene, N, the two ricinoleic acid amides of N '-ethylene, methyl hydroxystearate etc.; Said pigment can adopt general organic or inorganic pigment.
Usually can obtain polyolefin functionality special-purpose material of the present invention by following three kinds of methods.
(1) solution grafting: the batching according to above illustrating, except that initiator, all join in the xylene solvent, progressively be warming up to 90～125 ℃, all solids is all dissolved, form 5～15% solution.After drum nitrogen is got rid of oxygen, divide progressively to add initiator 3～5 times holding temperature reaction 3～4 hours.After reaction finishes, reaction solution is reduced to room temperature, solid is separated out, after filtration, dry back adds an amount of additive and promptly obtain functionality special-purpose material;
(2) fusion-grafting method: the batching according to above illustrating progressively joins in single screw extrusion machine or twin screw extruder or the Banbury mixer melting graft reaction under 170～210 ℃ of temperature after high-speed mixing.Reaction times is 1～15 minute.After reaction finishes, product is pulverized, water or acetone extract are removed the free polyethers, and dry back adds an amount of additive and promptly gets functionality special-purpose material;
(3) solid phase grafting method: according to the batching that above illustrates, at first polyolefin resin is ground into the powder more than 40 orders, except that initiator, all join in the high-speed mixer then and mix, join again in the reactor that is equipped with helix agitator, elevated temperature while stirring, reach 90～125 ℃ after, drum nitrogen is got rid of oxygen, divide initiator 3～5 times and progressively add reactor, react after 3～5 hours, reduce to room temperature.Water or acetone extract, dry back add an amount of additive and promptly obtain functionality special-purpose material.
This functionality special-purpose material and corresponding polyolefin blend can make polyolefine have good paintability, processibility and static resistance, and under the prerequisite that keeps rigidity and hardness, significantly improve the shock resistance of this material.This functionality special-purpose material can be as the higher trolley part of paintability and appearance requirement, polyolein fiber and the addition material that needs the plastics of external coating.
The present invention will be specifically described by the following example and Comparative Examples hereinafter, and the testing method that adopts in embodiment and Comparative Examples is as follows:
Hydroxy value measuring GB12008.3-89
Tensile strength GB/T1040-92
Flexural strength GB9341-88
Cantilever-type impact strength GB1843-80 (89)
Melt flow rate (MFR) ASTM D-1238
The test GB1410-89 of surface resistivity
Sticking power test GB9286-88
The evaluation of paintability is to be undertaken by the water resisting property of the paint film adhesion of measuring a specimen and another specimen.The coating process of sample is as follows:
Make a long 100mm with injection moulding machine, the thin plate of wide 140mm and thick 1mm is as test block, after oil removing is cleaned and activated, with the test panel scrub.After the drying, apply the thick paint film of one deck 23 ± 2 μ m, solidified 30 minutes down at 90 ℃ then with polyurethane coating.Coated thin plate was at room temperature placed 48 hours, obtained the test block (test block 1) of paintability.
The sticking power test:
On the coated membrane of the test block 1 that obtains with aforesaid method, mark the sub-box of many length of side 1mm equably with cutting knife, in cutting, require the edge of a knife just in time can penetrate paint film and touch ground.On sub-box, stick one deck adhesive plaster then.Power with a certain size is torn adhesive plaster, sees the degree that paint film is stripped from, and decides the rank of paint film adhesion by GB9286-88.
Water resisting property:
Test block 1 was soaked 48 hours in water, obtain test block 2,, measure the situation of being stripped from of test block 2 then by above-mentioned paint film adhesion testing method.
The resin combination that said functionality special-purpose material and corresponding polyolefin blend obtain, the quality of its antistatic property is weighed with the size of surface resistivity.
Embodiment 1
Get new LDPE (film grade) ZJ2600 (melt flow rate (MFR) 24g/10min, Shanghai petrochemical industry limited-liability company produces) 100g, the acrylate 20g of TriMethylolPropane(TMP) polyethers, hydroxyl value is 260, vinylbenzene 4g, 1010 oxidation inhibitor 0.05g join in the flask of 2000ml, add 1300g dimethylbenzene then, progressively be warming up to 100 ℃.After treating that solid all dissolves, get benzoyl peroxide 1.3g, divide in 4 hours to join in the flask for 5 times, keep 100 ℃ of reactions.After reaction finishes, flask is cooled to room temperature, adds 100g acetone, treat after the stirring that solid separates out fully from solution, promptly obtain the functionalization polyethylene special-purpose material after drying.Functionalization polyethylene special-purpose material hydroxyl value is 21.(numbering: 1#)
Embodiment 2
Get homo-polypropylene 1700# (melt flow rate (MFR) is 15g/10min, and Beijing Yanshan Petrochemical Company produces) 100g, obtain 45 purpose powder after crushed, add in the super mixer then.The methacrylic ester 25g that in mixing tank, adds the tetramethylolmethane polyethers again, hydroxyl value is 390, vinylbenzene 7g, 1010 oxidation inhibitor 0.05g, adding 1000ml behind the thorough mixing is equipped with in the reactor of helix agitator, be heated to 110 ℃ while stirring, match in twos after then benzoyl peroxide 1.0g and tertbutyl peroxide 0.3g respectively being divided into 5 parts, divide initiation graftings reaction in 5 input reactors in 3 hours.Use acetone after reaction finishes, in cable-styled extractor,, obtain functional polypropylene for special purpose after the drying powder extraction 10 hours.The functional polypropylene for special purpose hydroxyl value is 52.(numbering: 2#)
Embodiment 3
(melt flow rate (MFR) is 7g/10min to get Co-polypropylene M700R, the production of Shanghai petrochemical industry limited-liability company) 2.5 kilograms, the fumarate 630g of tetramethylolmethane polyethers, hydroxyl value is 320, vinylbenzene 130g, 1010 oxidation inhibitor 1.6g, benzoyl peroxide 0.8g, dicumyl peroxide 4g all puts into high-speed mixer mixing 1min, discharging.Compound is put into φ 35 single screw extrusion machines, extrude with the speed responsing of 50rpm.Extruding product pulverizes after 10 hours after drying of acetone extract obtain functional polypropylene for special purpose.The functional polypropylene for special purpose hydroxyl value is 48.(numbering: 3#)
Below be prepared polyolefin functionality special-purpose material implementation result example:
Embodiment 4
Ethylene-octene copolymer elastomer (ENGAGE 8150#) with U.S. DOW chemical company is a comparison, and specimen coding is A.2.3 kilograms on 8150# elastomerics, 1# functionality special-purpose material 200g, 1010 oxidation inhibitor 13g, in φ 35 twin screw extruders, 180 ℃ of following mixing granulators obtain the modified elastomer material, are numbered A '.Both mechanical properties and antistatic property are as follows:
Sample melt flow rate (MFR) tensile strength extension at break surface resistivity
G/10min MPa % (relative humidity 70%)
A 0.5 11.3 790 1.9×10
16
A′ 0.8 15.7 780 4.7×10
10
Embodiment 5
With the polypropylene 1700# of Beijing Yanshan Petrochemical Company is comparison, is numbered B.Get the 1700#2.3 kilogram, 2# functionality special-purpose material 200g, 1010 oxidation inhibitor 13g, in φ 35 twin screw extruders, 175 ℃ of following mixing granulators obtain the modified polypropene material, are numbered B '.Both mechanics, antistatic property and paintability are as follows:
Sample tensile strength flexural strength shock strength surface resistivity paint film tack
MPa MPa J/m (relative humidity 70%)
37.7 41.1 24 3.2 * 1,016 5 grades of B
40.2 40.9 37 3.6 * 1,010 1 grades of B '
Embodiment 6
The block copolymerization polypropylene (trade mark: M2101R) be comparison, be numbered C with Shanghai petrochemical industry limited-liability company.Get the M2101R2.35 kilogram, 3# functionality special-purpose material 150g, 1010 oxidation inhibitor 13g, in φ 35 twin screw extruders, 185 ℃ of following mixing granulators obtain the modified polypropene material, are numbered C '.Both mechanical properties, static resistance and paintability are as follows:
Sample tensile strength flexural strength shock strength surface resistivity paint film tack
MPa MPa J/m (relative humidity 70%)
C 19.6 42.9 63.7 2.7 * 10
165 grades
C ' 21.2 41.7 82.5 2.4 * 10
101 grade
From top example as can be seen,, add in the corresponding polyolefin substrate, can improve the paintability of material, keep and improve material mechanical performance, have good comprehensive performances prepared functionality special-purpose material.
Claims (5)
1. a new type polyolefin functionality special-purpose material is characterized in that, said PP Pipe Compound is performed such preparation:
The polyolefin resin of 60～95 weight %, the multi-hydroxy polyether of 5～40 weight %, the vinylbenzene of 1.0～5.0 weight % and the oxidation inhibitor of 0.02～1.0 weight % are joined in the xylene solvent, be warming up to 90～125 ℃, dissolving forms 5～15% solution, the initiator that adds 0.2～5.0 weight % behind the drum nitrogen eliminating oxygen, reacted 3～4 hours, solid is separated out in cooling, after filtration, promptly obtain functionality special-purpose material after the drying; Weight percent is a benchmark with the total amount of polyolefin resin and multi-hydroxy polyether all;
Wherein: the structural formula of said multi-hydroxy polyether is as follows, and its hydroxyl value scope contains 1～3 activity double key 100～700,
In the formula: n=4～20, R
1Be the polyvalent alcohol end group, comprise: propylene glycol, ethylene glycol, glycerol, pentanediol, hexylene glycol, tetramethylolmethane, TriMethylolPropane(TMP) or butantetraol; R
2For-H or-CH
3, R
3For containing the group of active unsaturated double-bond, comprise the surplus portion of vinylformic acid, methacrylic acid, toxilic acid, fumaric acid, Hydroxyethyl acrylate or hydroxyethyl methylacrylate;
Said oxidation inhibitor is 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, 2,4, one or more in 6-tri-butyl-phenol, Tyox B, thio-2 acid two (octadecyl ester), thio-2 acid two (14 ester), antioxidant 1010 or the antioxidant CA;
Said initiator is one or more in dicumyl peroxide, benzoyl peroxide, dilauroyl peroxide, ditertiary butyl peroxide, tertbutyl peroxide, the tert butyl peroxy benzoate.
2. a new type polyolefin functionality special-purpose material is characterized in that, said PP Pipe Compound is performed such preparation:
At first the polyolefin resin of 60～95 weight % is ground into the powder more than 40 orders, together with the multi-hydroxy polyether of 5～40 weight %, the vinylbenzene of 1.0～5.0 weight % and the oxidation inhibitor of 0.02～1.0 weight %, join in the mixing machine and mix, join then in the reactor that is equipped with helix agitator, after stirring heats up and reaches 90～125 ℃, drum nitrogen is got rid of oxygen, the initiator of 0.2～5.0 weight % is added reactor, react after 3～5 hours, promptly obtain functionality special-purpose material after extraction, the drying; Weight percent is a benchmark with the total amount of component polyolefin resin and multi-hydroxy polyether all;
Wherein: the structural formula of said multi-hydroxy polyether is as follows, and its hydroxyl value scope contains 1～3 activity double key 100～700,
In the formula: n=4～20, R
1Be the polyvalent alcohol end group, comprise: propylene glycol, ethylene glycol, glycerol, pentanediol, hexylene glycol, tetramethylolmethane, TriMethylolPropane(TMP) or butantetraol; R
2For-H or-CH
3, R
3For containing the group of active unsaturated double-bond, comprise the surplus portion of vinylformic acid, methacrylic acid, toxilic acid, fumaric acid, Hydroxyethyl acrylate or hydroxyethyl methylacrylate;
Said oxidation inhibitor is 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, 2,4, one or more in 6-tri-butyl-phenol, Tyox B, thio-2 acid two (octadecyl ester), thio-2 acid two (14 ester), antioxidant 1010 or the antioxidant CA;
Said initiator is one or more in dicumyl peroxide, benzoyl peroxide, dilauroyl peroxide, ditertiary butyl peroxide, tertbutyl peroxide, the tert butyl peroxy benzoate.
3. a new type polyolefin functionality special-purpose material is characterized in that, said PP Pipe Compound is performed such preparation:
The polyolefin resin of 60～95 weight %, the multi-hydroxy polyether of 5～40 weight %, the vinylbenzene of 1.0～5.0 weight %, the oxidation inhibitor of 0.02～1.0 weight % and the initiator of 0.2～5.0 weight % are progressively joined after high-speed mixing in single screw extrusion machine or twin screw extruder or the Banbury mixer, melting graft reaction under 170～210 ℃ of temperature, reaction times is 1～15 minute, remove the free polyethers, promptly get functionality special-purpose material after the drying; Weight percent is a benchmark with the total amount of component polyolefin resin and multi-hydroxy polyether all;
Wherein: said polyolefin resin melt flow rate (MFR) is 4～40g/10min;
The structural formula of said multi-hydroxy polyether is as follows, and its hydroxyl value scope contains 1～3 activity double key 100～700,
In the formula: n=4～20, R
1Be the polyvalent alcohol end group, comprise: propylene glycol, ethylene glycol, glycerol, pentanediol, hexylene glycol, tetramethylolmethane, TriMethylolPropane(TMP) or butantetraol; R
2For-H or-CH
3, R
3For containing the group of active unsaturated double-bond, comprise the surplus portion of vinylformic acid, methacrylic acid, toxilic acid, fumaric acid, Hydroxyethyl acrylate or hydroxyethyl methylacrylate;
Said oxidation inhibitor is 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, 2,4, one or more in 6-tri-butyl-phenol, Tyox B, thio-2 acid two (octadecyl ester), thio-2 acid two (14 ester), antioxidant 1010 or the antioxidant CA;
Said initiator is one or more in dicumyl peroxide, benzoyl peroxide, dilauroyl peroxide, ditertiary butyl peroxide, tertbutyl peroxide, the tert butyl peroxy benzoate.
4. functionality special-purpose material as claimed in claim 1 is characterized in that: comprise also in the batching that additive, said additive are one or more in UV stabilizer, lubricant or the pigment.
5. as claim 2 or 3 described functionality special-purpose materials, it is characterized in that: comprise also in the batching that additive, said additive are one or more in UV stabilizer, lubricant or the pigment.
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|---|---|---|---|
| CNB99116895XA CN1183175C (en) | 1999-09-23 | 1999-09-23 | New type polyolefin functionality special-purpose material |
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|---|---|---|---|
| CNB99116895XA CN1183175C (en) | 1999-09-23 | 1999-09-23 | New type polyolefin functionality special-purpose material |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100443519C (en) * | 2006-09-06 | 2008-12-17 | 江苏创源科技新材料有限公司 | Fusion graft process for modified polypropylene/acrylic acid polyester ether |
| CN101016360B (en) * | 2007-01-18 | 2010-05-19 | 武汉工程大学 | Solid phase preparation method for simultaneously increasing polarity and graft degree of polyolefin |
| CN101805458B (en) * | 2010-04-07 | 2012-02-08 | 天津力生化工有限公司 | Method for preparing emulsion composite antioxidant |
| CN104059197B (en) * | 2013-03-22 | 2016-05-11 | 苏州克莱明新材料有限公司 | Polypropylene fusion graft vinyl ethers and preparation method thereof |
| CN105061681A (en) * | 2015-09-01 | 2015-11-18 | 南通拜林新材料科技有限公司 | Polyethylene modified through vinyl ether melt grafting and preparing method thereof |
| CN106188546A (en) * | 2016-07-20 | 2016-12-07 | 上海玉城高分子材料股份有限公司 | A kind of polystyrene anti-impact plasticized modifier and preparation method thereof |
| CN115400684A (en) * | 2022-08-01 | 2022-11-29 | 奥美凯聚合物（苏州）有限公司 | Preparation device and method of outdoor polypropylene product with high weather resistance and high chroma |
| CN115386167B (en) * | 2022-09-27 | 2023-08-22 | 上海金发科技发展有限公司 | Polypropylene composition and preparation method and application thereof |
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