CN107383740A - A kind of PP/COC alloy materials and preparation method thereof of high intensity, low-shrinkage - Google Patents
A kind of PP/COC alloy materials and preparation method thereof of high intensity, low-shrinkage Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
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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
- B29C48/25—Component parts, details or accessories; Auxiliary operations
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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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
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Abstract
The present invention relates to technical field of polymer materials, and in particular to a kind of high intensity, the PP/COC alloy materials and preparation method thereof of low-shrinkage.The alloy material includes the raw material of following parts by weight：20 80 parts of polypropylene, 20 50 parts of cyclic olefine copolymers, 15 parts of compatilizers, 15 parts of toughener, 0.1 0.5 parts of dispersants, 0.2 0.8 parts of lubricants and 0.1 0.3 parts of antioxidants.The PP/COC alloy materials intensity of the present invention is high, shrinkage factor is low, good stability of the dimension, and with performances such as preferable toughness, corrosion resistance, wearability, oil resistivity and impact resistances, processability is good, and processing characteristics is good, and cost is low, and use value is high；The preparation method of the present invention, the preparation method is simple, convenient operation and control, steady quality, and production efficiency is high, and production cost is low, is adapted to large-scale industrial production.
Description
Technical field
The present invention relates to technical field of polymer materials, and in particular to a kind of high intensity, the PP/COC alloys of low-shrinkage
Material and preparation method thereof.
Background technology
Polypropylene（PP）It is one of plastic material commonly used in present plastics market, its density is low, cost is low, makes polypropylene
Material has certain plastic applications scope.
But polyacrylic intensity is relatively low simultaneously, and shrinkage factor is big, and dimensional stability is low so that utilizes product made from polypropylene
The problems such as surface easily scratches be present, polypropylene is more difficult to widen the market of other field, polyacrylic use is caused to limit.
But method of modifying many at present, is required for adding substantial amounts of auxiliary agent, and the addition of inorganic lubricant filler can influence the toughness of material,
The addition of toughener can influence heat endurance, wearability and decay resistance of material etc..
The content of the invention
In order to overcome shortcoming and defect present in prior art, it is an object of the invention to provide a kind of high intensity, low
The PP/COC alloy materials of shrinkage factor, the PP/COC alloy materials intensity is high, shrinkage factor is low, good stability of the dimension, and with compared with
The performances such as good toughness, wearability, corrosion resistance and heat endurance, use value are high.
Another object of the present invention is to provide a kind of high intensity, low-shrinkage PP/COC alloy materials preparation side
Method, the preparation method is simple, convenient operation and control, steady quality, and production efficiency is high, and production cost is low, is adapted to large-scale industry
Metaplasia is produced.
The purpose of the present invention is achieved through the following technical solutions：A kind of PP/COC alloy materials of high intensity, low-shrinkage
And preparation method thereof, the alloy material includes the raw material of following parts by weight：
Polypropylene 20-80 parts
Cyclic olefine copolymer 20-50 parts
Compatilizer 1-5 parts
Toughener 1-5 parts
Dispersant 0.1-0.5 parts
Lubricant 0.2-0.8 parts
Antioxidant 0.1-0.3 parts.
The PP/COC alloy materials of the present invention by using above-mentioned raw materials, between each raw material mutual cooperation act on, collaboration is anti-
Should, it can make obtained PP/COC alloy materials that there is higher intensity, relatively low shrinkage factor, and good stability of the dimension, and have
The performances such as preferable toughness, corrosion resistance, wearability, oil resistivity and impact resistance, processability is good, and processing characteristics is good, cost
Low, use value is high, solves the problems such as strength of PP is relatively low, shrinkage factor is big, dimensional stability is low, surface easily scratches；Together
When there is relatively low water absorption rate, make PP/COC alloy material materials that still there is excellent size and physical in wet environment
Can, good stability of the dimension, original size and physical property will not be changed because of wet environment, widen polyacrylic applicable model
Enclose.
Wherein, by using compatilizer, the interfacial tension between each raw material is reduced, improves the interface between each raw material
Bonding force, improve the compatible role of PP/COC alloy material materials；By using toughener, PP/COC alloy materials are improved
Toughness, intensity, wearability, the performance such as impact resistance；By using dispersant, each raw material of PP/COC alloy materials can be made abundant
Dispersion mixing, and then make each raw material play maximum performance effect, make obtained PP/COC alloy materials have preferable toughness,
The performances such as corrosion resistance, wearability, oil resistivity and impact resistance；By using lubricant, PP/COC alloy materials are played interior
Portion lubricates and the effect of external lubrication, improves the processability and processing characteristics of PP/COC alloy materials；By using antioxygen
Agent, the thermal-oxidative degradation degree of PP/COC alloy materials can be effectively reduced, preferable mechanical property can be kept for a long time.
Preferably, the cyclic olefine copolymer be molecular weight 4000-50000, the degree of polymerization 200-800 amorphism ring
Olefin copolymer.The present invention is by using specified molecular weight and the cycloolefin copolymer of specific aggregation degree, and water absorption rate is low, shrinkage factor
It is low, good stability of the dimension, and there is excellent intensity, toughness and impact resistance, effectively improve PP/COC alloy materials toughness,
The performances such as intensity, wearability, impact resistance.
Preferably, the compatilizer is cyclic acid anhydride type compatilizer, carboxylic acid type compatilizer, epoxide resin type compatilizer, evil
At least one of oxazoline type compatilizer, imide-type compatilizer and isocyanate-based compatilizer.
Preferably, the cyclic acid anhydride type compatilizer is maleic anhydride stem grafting polyolefin, and the carboxylic acid type compatilizer is second
Alkene-esters of acrylic acid ter-polymers grafting ethylene oxidic ester, the oxazoline type compatilizer is oxazoline grafted polystyrene,
The acid amide type compatilizer is sub- amide modifications acrylate, and the isocyanate-based compatilizer is m- isopropenyl -2,2- bis-
Methyl benzoyl isocyanates.
The present invention can effectively reduce the interfacial tension of PP, COC between the two, carry by using the compatilizer of mentioned kind
Interface cohesive force between high PP, COC, and then improve the compatible role of PP/COC alloy materials.It is more highly preferred to, the phase
It is that ethylene-acrylic acid esters ter-polymers are grafted ethylene oxidic ester, oxazoline grafted polystyrene and sub- amide modifications to hold agent
Acrylate is using weight ratio as 2.4-3.2:1:1.2-1.8 the mixture of composition.
Preferably, the toughener is methyl methacrylate-butadiene-styrene copolymer, acrylic nitrile-butadiene
Diene-styrene copolymer, haloflex, ethylene-vinyl acetate copolymer, polyvinyl butyral resin, styrene-fourth two
At least one of thermoplastic olefinic elastomer and polyimides.
The present invention can be effectively increased the toughness of PP/COC alloy materials, reduce easy by using the toughener of mentioned kind
Fragility, the intensity of PP/COC alloy materials is improved, solves the problems, such as that strength of PP is low；It is more highly preferred to, the toughener
It is acrylonitrile-butadiene-styrene copolymer, haloflex and polyimides using weight ratio as 1:1.2-1.8：2.5-3.5
The mixture of composition.
Preferably, the dispersant be carmethose, polyoxypropylene, polyoxyethylene copolymer, alkyl polyoxyethylene,
In polyethenoxy ether, neopelex, Sodium Polyacrylate, sodium polymethacrylate, sulfonated polyaniline and sodium taurocholate
It is at least one.
The present invention can promote mutually dividing for each reaction raw materials of PP/COC alloy materials by using the dispersant of mentioned kind
Dissipate property, and then improve the mixing uniformity of each raw material, make obtained PP/COC alloy materials be respectively provided with preferable toughness, intensity,
The performances such as wearability, impact resistance；It is more highly preferred to, the dispersant is neopelex, Sodium Polyacrylate and gathered
Oxypropylene ether is using weight ratio as 2.5-3.5：1.4-2.2:The mixture of 1 composition.
Preferably, the lubricant is stearic amide, N, N '-ethylenebisstearamide, n-butyl stearate, glycerine
At least one of three hydroxy stearic acid esters, Tissuemat E, polymethylphenyl siloxane fluid, ethylene bis stearamide and zinc stearate.
The present invention plays internal lubrication and external lubrication by using the lubricant of mentioned kind to PP/COC alloy materials
Effect, improve the processing characteristicies of PP/COC alloy materials.；It is more highly preferred to, the lubricant is n-butyl stearate, sweet
Oily three hydroxy stearic acid esters and N, N '-ethylenebisstearamide is using weight ratio as 0.8-1.2：2.4-3.2:The mixture of 1 composition.
Preferably, the antioxidant is the double -3- of triethylene glycol（3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls）Acrylate,
N, N '-hexamethylene bis（3,5- di-t-butyl -4- hydroxyl hydrocinnamamides）, 1,3,5-three (3,5 di-t-butyl-4- hydroxy benzenes
Base) isocyanates, three (2,4- di-tert-butyl-phenyl) phosphite esters, 1,3,5- tri-（3,5 tertiary butyl-4-hydroxy benzyls）Trimethyl
Benzene, β（3,5 di-t-butyl-4-hydroxy phenyl) at least one of propionic acid octadecyl and 2,6 BHTs.
Antioxidant of the invention by using mentioned kind, it can effectively reduce the thermal-oxidative degradation journey of PP/COC alloy materials
Degree, the hydrolysis and degraded for effectively avoiding PP, COC from occurring at high temperature by the presence of minor amount of water, and improve PP, COC antioxygen
The property changed, makes PP/COC alloy materials have preferable inoxidizability, extends service life；It is more highly preferred to, it is described anti-oxidant
Agent is N, N '-hexamethylene bis（3,5- di-t-butyl -4- hydroxyl hydrocinnamamides）, 1,3,5-three (3,5 di-t-butyl-4- hydroxyls
Phenyl) isocyanates and 2,6 BHTs are using weight ratio as 2.4-3.2:1.2-1.8：The mixture of 1 composition.
Another object of the present invention is achieved through the following technical solutions：A kind of above-mentioned high intensity, the PP/ of low-shrinkage
The preparation method of COC alloy materials, comprises the following steps：Raw material is weighed according to parts by weight, and is mixed, then through squeezing
Go out equipment to be melted, extruded, be granulated, obtain high intensity, the PP/COC alloy materials of low-shrinkage.
The preparation method of the present invention is simple, convenient operation and control, steady quality, and production efficiency is high, and production cost is low, is adapted to
Large-scale industrial production.
Preferably, the mixing rotating speed of the mixing is 400-800r/min, incorporation time 3-5min；The extrusion
One area's temperature of equipment is 260-270 DEG C, and two area's temperature are 265-275 DEG C, and three area's temperature are 275-285 DEG C, and four area's temperature are
275-285 DEG C, five area's temperature are 275-285 DEG C, and six area's temperature are 270-280 DEG C.
Mixing rotating speed, incorporation time and extrusion temperature of the invention by strictly controlling raw material, obtained PP/ can be made
COC alloy materials have higher intensity, a relatively low shrinkage factor, good stability of the dimension, and with preferable toughness, corrosion-resistant
Property, the performance such as wearability, oil resistivity and impact resistance, solve that strength of PP is low, shrinkage factor is big, dimensional stability is low, production
The problems such as product surface easily scratches.
The beneficial effects of the present invention are：The PP/COC alloy materials intensity of the present invention is high, shrinkage factor is low, dimensional stability
It is good, and with performances such as preferable toughness, corrosion resistance, wearability, oil resistivity and impact resistances, solve product and surface be present
The problems such as easily scratching, and processability is good, processing characteristics is good, and cost is low, and use value is high, and use range is extensive.
The PP/COC alloy materials of the present invention reduce the interfacial tension between each raw material, improved by using compatilizer
Interface cohesive force between each raw material, improve the compatible role of PP/COC alloy material materials；By using toughener, carry
The performances such as the high toughness of PP/COC alloy materials, intensity, wearability, impact resistance；By using dispersant, PP/COC can be made
The fully dispersed mixing of each raw material of alloy material, and then each raw material is played maximum performance effect, make obtained PP/COC alloys
Material has the performances such as preferable toughness, corrosion resistance, wearability, oil resistivity and impact resistance；It is right by using lubricant
PP/COC alloy materials play a part of internal lubrication and external lubrication, improve the processability of PP/COC alloy materials and add
Work performance；By using antioxidant, can effectively reduce the thermal-oxidative degradation degree of PP/COC alloy materials, can keep for a long time compared with
Good mechanical property.
The preparation method of the present invention, the preparation method is simple, convenient operation and control, steady quality, and production efficiency is high, production
Cost is low, is adapted to large-scale industrial production.
Embodiment
For the ease of the understanding of those skilled in the art, with reference to embodiment, the present invention is further illustrated, real
The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
The PP/COC alloy materials and preparation method thereof of a kind of high intensity, low-shrinkage, the alloy material includes following parts by weight
Raw material：
20 parts of polypropylene
50 parts of cyclic olefine copolymer
1 part of compatilizer
1 part of toughener
0.1 part of dispersant
0.2 part of lubricant
0.1 part of antioxidant.
The cyclic olefine copolymer is molecular weight in amorphism cyclic olefine copolymer of the 4000, degree of polymerization 800.
The compatilizer is cyclic acid anhydride type compatilizer, and the cyclic acid anhydride type compatilizer is maleic anhydride grafted polyolefin
Hydrocarbon.
The toughener is methyl methacrylate-butadiene-styrene copolymer.
The dispersant is at least one of carmethose and polyoxypropylene.
The lubricant is stearic amide.
The antioxidant is β（3,5 di-t-butyl-4-hydroxy phenyl) propionic acid octadecyl.
A kind of above-mentioned high intensity, low-shrinkage PP/COC alloy materials preparation method, comprise the following steps：According to
Parts by weight weigh raw material, and are mixed, and then extruded equipment is melted, extruded, is granulated, and obtain high intensity, low
The PP/COC alloy materials of shrinkage factor.
The mixing rotating speed of the mixing is 400/min, incorporation time 5min；
One area's temperature of the extrusion equipment is 260 DEG C, and two area's temperature are 265 DEG C, and three area's temperature are 275 DEG C, and four area's temperature are
285 DEG C, five area's temperature are 275 DEG C, and six area's temperature are 270 DEG C.
Embodiment 2
The PP/COC alloy materials and preparation method thereof of a kind of high intensity, low-shrinkage, the alloy material includes following parts by weight
Raw material：
35 parts of polypropylene
42 parts of cyclic olefine copolymer
2 parts of compatilizer
2 parts of toughener
0.2 part of dispersant
0.35 part of lubricant
0.15 part of antioxidant.
The cyclic olefine copolymer is molecular weight in amorphism cyclic olefine copolymer of the 15500, degree of polymerization 650.
The compatilizer is carboxylic acid type compatilizer, and the carboxylic acid type compatilizer is ethylene-acrylic acid esters ter-polymers
It is grafted ethylene oxidic ester.
The toughener is at least one of styrene butadiene thermoplasticelastomer and polyimides.
The dispersant is at least one of polyoxyethylene copolymer and alkyl polyoxyethylene.
The lubricant is the hydroxy stearic acid ester of glycerine three.
The antioxidant is N, N '-hexamethylene bis（3,5- di-t-butyl -4- hydroxyl hydrocinnamamides）.
A kind of above-mentioned high intensity, low-shrinkage PP/COC alloy materials preparation method, comprise the following steps：According to
Parts by weight weigh raw material, and are mixed, and then extruded equipment is melted, extruded, is granulated, and obtain high intensity, low
The PP/COC alloy materials of shrinkage factor.
The mixing rotating speed of the mixing is 500r/min, incorporation time 4.5min；
One area's temperature of the extrusion equipment is 262 DEG C, and two area's temperature are 268 DEG C, and three area's temperature are 278 DEG C, and four area's temperature are
283 DEG C, five area's temperature are 278 DEG C, and six area's temperature are 272 DEG C.
Embodiment 3
The PP/COC alloy materials and preparation method thereof of a kind of high intensity, low-shrinkage, the alloy material includes following parts by weight
Raw material：
50 parts of polypropylene
35 parts of cyclic olefine copolymer
3 parts of compatilizer
3 parts of toughener
0.3 part of dispersant
0.5 part of lubricant
0.2 part of antioxidant.
The cyclic olefine copolymer is molecular weight in amorphism cyclic olefine copolymer of the 26500, degree of polymerization 500.
The compatilizer is oxazoline type compatilizer, and the oxazoline type compatilizer is oxazoline grafted polystyrene.
The toughener is at least one of acrylonitrile-butadiene-styrene copolymer and haloflex.
The dispersant is at least one of polyethenoxy ether and neopelex.
The lubricant is N, N '-at least one of ethylenebisstearamide and n-butyl stearate.
The antioxidant is the double -3- of triethylene glycol（3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls）Acrylate and 1,3,5-
Three（3,5 tertiary butyl-4-hydroxy benzyls）At least one of trimethylbenzene.
A kind of above-mentioned high intensity, low-shrinkage PP/COC alloy materials preparation method, comprise the following steps：According to
Parts by weight weigh raw material, and are mixed, and then extruded equipment is melted, extruded, is granulated, and obtain high intensity, low
The PP/COC alloy materials of shrinkage factor.
The mixing rotating speed of the mixing is 600r/min, incorporation time 4min；
One area's temperature of the extrusion equipment is 265 DEG C, and two area's temperature are 270 DEG C, and three area's temperature are 280 DEG C, and four area's temperature are
280 DEG C, five area's temperature are 280 DEG C, and six area's temperature are 275 DEG C.
Embodiment 4
The PP/COC alloy materials and preparation method thereof of a kind of high intensity, low-shrinkage, the alloy material includes following parts by weight
Raw material：
65 parts of polypropylene
27 parts of cyclic olefine copolymer
4 parts of compatilizer
4 parts of toughener
0.4 part of dispersant
0.65 part of lubricant
0.25 part of antioxidant.
The cyclic olefine copolymer is molecular weight in amorphism cyclic olefine copolymer of the 38000, degree of polymerization 350.
The compatilizer is imide-type compatilizer, and the imide-type compatilizer is sub- amide modifications acrylate.
The toughener is at least one of ethylene-vinyl acetate copolymer and polyvinyl butyral resin.
The dispersant is at least one of Sodium Polyacrylate and sodium polymethacrylate.
The lubricant is at least one of Tissuemat E and polymethylphenyl siloxane fluid.
The antioxidant is three (2,4- di-tert-butyl-phenyl) phosphite esters and 2, in 6 BHTs at least
It is a kind of.
A kind of above-mentioned high intensity, low-shrinkage PP/COC alloy materials preparation method, comprise the following steps：According to
Parts by weight weigh raw material, and are mixed, and then extruded equipment is melted, extruded, is granulated, and obtain high intensity, low
The PP/COC alloy materials of shrinkage factor.
The mixing rotating speed of the mixing is 700r/min, incorporation time 3.5min；
One area's temperature of the extrusion equipment is 268 DEG C, and two area's temperature are 273 DEG C, and three area's temperature are 283 DEG C, and four area's temperature are
278 DEG C, five area's temperature are 283 DEG C, and six area's temperature are 278 DEG C.
Embodiment 5
The PP/COC alloy materials and preparation method thereof of a kind of high intensity, low-shrinkage, the alloy material includes following parts by weight
Raw material：
80 parts of polypropylene
20 parts of cyclic olefine copolymer
5 parts of compatilizer
5 parts of toughener
0.5 part of dispersant
0.8 part of lubricant
0.3 part of antioxidant.
The cyclic olefine copolymer is molecular weight in amorphism cyclic olefine copolymer of the 50000, degree of polymerization 200.
The compatilizer is isocyanate-based compatilizer, and the isocyanate-based compatilizer is m- isopropenyl -2,2- bis-
Methyl benzoyl isocyanates.
The toughener is polyimides.
The dispersant is at least one of sulfonated polyaniline and sodium taurocholate.
The lubricant is at least one of ethylene bis stearamide and zinc stearate.
The antioxidant is 1,3,5-three (3,5 di-tert-butyl-hydroxy phenyl) isocyanates.
A kind of above-mentioned high intensity, low-shrinkage PP/COC alloy materials preparation method, comprise the following steps：According to
Parts by weight weigh raw material, and are mixed, and then extruded equipment is melted, extruded, is granulated, and obtain high intensity, low
The PP/COC alloy materials of shrinkage factor.
The mixing rotating speed of the mixing is 800r/min, incorporation time 3min；
One area's temperature of the extrusion equipment is 270 DEG C, and two area's temperature are 275 DEG C, and three area's temperature are 285 DEG C, and four area's temperature are
275 DEG C, five area's temperature are 285 DEG C, and six area's temperature are 280 DEG C.
Embodiment 6
The difference of the present embodiment and above-described embodiment 1 is：
The compatilizer be ethylene-acrylic acid esters ter-polymers be grafted ethylene oxidic ester, oxazoline grafted polystyrene and
Sub- amide modifications acrylate is using weight ratio as 2.4:1:The mixture of 1.2 compositions.
The toughener be acrylonitrile-butadiene-styrene copolymer, haloflex and polyimides using weight ratio as
1: 1.8：3.5 the mixture of composition.
The dispersant is neopelex, Sodium Polyacrylate and polyethenoxy ether using weight ratio as 2.5：2.2:
The mixture of 1 composition.
The lubricant is n-butyl stearate, the hydroxy stearic acid ester of glycerine three and N, N '-ethylenebisstearamide is with weight
Amount is than being 0.8：2.4:The mixture of 1 composition.
The antioxidant is N, N '-hexamethylene bis（3,5- di-t-butyl -4- hydroxyl hydrocinnamamides）, 1,3,5-three
(3,5 di-tert-butyl-hydroxy phenyl) isocyanates and 2,6 BHTs are using weight ratio as 2.4:1.8：1 composition
Mixture.
Embodiment 7
The difference of the present embodiment and above-described embodiment 2 is：
The compatilizer be ethylene-acrylic acid esters ter-polymers be grafted ethylene oxidic ester, oxazoline grafted polystyrene and
Sub- amide modifications acrylate is using weight ratio as 2.6:1:The mixture of 1.3 compositions.
The toughener be acrylonitrile-butadiene-styrene copolymer, haloflex and polyimides using weight ratio as
1:1.6：The mixture of 3.2 compositions.
The dispersant is neopelex, Sodium Polyacrylate and polyethenoxy ether using weight ratio as 2.8：2:1
The mixture of composition.
The lubricant is n-butyl stearate, the hydroxy stearic acid ester of glycerine three and N, N '-ethylenebisstearamide is with weight
Amount is than being 0.9：2.6:The mixture of 1 composition.
The antioxidant is N, N '-hexamethylene bis（3,5- di-t-butyl -4- hydroxyl hydrocinnamamides）, 1,3,5-three
(3,5 di-tert-butyl-hydroxy phenyl) isocyanates and 2,6 BHTs are using weight ratio as 2.6:1.6：1 composition
Mixture.
Embodiment 8
The difference of the present embodiment and above-described embodiment 3 is：
The compatilizer be ethylene-acrylic acid esters ter-polymers be grafted ethylene oxidic ester, oxazoline grafted polystyrene and
Sub- amide modifications acrylate is using weight ratio as 2.8:1:The mixture of 1.5 compositions.
The toughener be acrylonitrile-butadiene-styrene copolymer, haloflex and polyimides using weight ratio as
1:1.5：The mixture of 3 compositions.
The dispersant is neopelex, Sodium Polyacrylate and polyethenoxy ether using weight ratio as 3：1.8:1
The mixture of composition.
The lubricant is n-butyl stearate, the hydroxy stearic acid ester of glycerine three and N, N '-ethylenebisstearamide is with weight
Amount is than being 1：2.8:The mixture of 1 composition.
The antioxidant is N, N '-hexamethylene bis（3,5- di-t-butyl -4- hydroxyl hydrocinnamamides）, 1,3,5-three
(3,5 di-tert-butyl-hydroxy phenyl) isocyanates and 2,6 BHTs are using weight ratio as 2.8:1.5：1 composition
Mixture.
Embodiment 9
The difference of the present embodiment and above-described embodiment 4 is：
The compatilizer be ethylene-acrylic acid esters ter-polymers be grafted ethylene oxidic ester, oxazoline grafted polystyrene and
Sub- amide modifications acrylate is using weight ratio as 3:1:The mixture of 1.6 compositions.
The toughener be acrylonitrile-butadiene-styrene copolymer, haloflex and polyimides using weight ratio as
1:1.3：The mixture of 2.8 compositions.
The dispersant is neopelex, Sodium Polyacrylate and polyethenoxy ether using weight ratio as 3.2：1.6:
The mixture of 1 composition.
The lubricant is n-butyl stearate, the hydroxy stearic acid ester of glycerine three and N, N '-ethylenebisstearamide is with weight
Amount is than being 1.1：3:The mixture of 1 composition.
The antioxidant is N, N '-hexamethylene bis（3,5- di-t-butyl -4- hydroxyl hydrocinnamamides）, 1,3,5-three
(3,5 di-tert-butyl-hydroxy phenyl) isocyanates and 2,6 BHTs are using weight ratio as 3:1.3：1 composition mixes
Compound.
Embodiment 10
The difference of the present embodiment and above-described embodiment 5 is：
The compatilizer be ethylene-acrylic acid esters ter-polymers be grafted ethylene oxidic ester, oxazoline grafted polystyrene and
Sub- amide modifications acrylate is using weight ratio as 3.2:1:The mixture of 1.8 compositions.
The toughener be acrylonitrile-butadiene-styrene copolymer, haloflex and polyimides using weight ratio as
1:1.2：The mixture of 2.5 compositions.
The dispersant is neopelex, Sodium Polyacrylate and polyethenoxy ether using weight ratio as 3.5：1.4:
The mixture of 1 composition.
The lubricant is n-butyl stearate, the hydroxy stearic acid ester of glycerine three and N, N '-ethylenebisstearamide is with weight
Amount is than being 1.2：3.2:The mixture of 1 composition.
The antioxidant is N, N '-hexamethylene bis（3,5- di-t-butyl -4- hydroxyl hydrocinnamamides）, 1,3,5-three
(3,5 di-tert-butyl-hydroxy phenyl) isocyanates and 2,6 BHTs are using weight ratio as 3.2:1.2：1 composition
Mixture.
Comparative example 1
A kind of PP is material modified and preparation method thereof, the material modified raw material for including following parts by weight：
50 parts of polypropylene
3 parts of compatilizer
3 parts of toughener
0.3 part of dispersant
0.5 part of lubricant
0.2 part of antioxidant.
The compatilizer is oxazoline type compatilizer, and the oxazoline type compatilizer is oxazoline grafted polystyrene.
The toughener is at least one of acrylonitrile-butadiene-styrene copolymer and haloflex.
The dispersant is at least one of polyethenoxy ether and neopelex.
The lubricant is N, N '-at least one of ethylenebisstearamide and n-butyl stearate.
The antioxidant is the double -3- of triethylene glycol（3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls）Acrylate and 1,3,5-
Three（3,5 tertiary butyl-4-hydroxy benzyls）At least one of trimethylbenzene.
Preparation method material modified a kind of above-mentioned PP, comprises the following steps：Raw material is weighed according to parts by weight, and is carried out
Mix, then extruded equipment is melted, extruded, is granulated, and it is material modified to obtain PP.
The mixing rotating speed of the mixing is 600r/min, incorporation time 4min；
One area's temperature of the extrusion equipment is 265 DEG C, and two area's temperature are 270 DEG C, and three area's temperature are 280 DEG C, and four area's temperature are
280 DEG C, five area's temperature are 280 DEG C, and six area's temperature are 275 DEG C.
Sample made from above-described embodiment 1-10 and comparative example 1 is positioned in air dry oven, dries 3- at 120 DEG C
4h, the above-mentioned sample after baking is then molded into iso standard batten with injection machine, each performance, performance are measured after being cooled to room temperature
Test result is as shown in the table.
From upper table data, PP/COC alloy materials intensity of the invention is high, shrinkage factor is low, good stability of the dimension, and
With performances such as preferable toughness, corrosion resistance, wearability, oil resistivity and impact resistances, solve product and surface be present and easily draw
The problems such as hindering, and processability is good, processing characteristics is good, and cost is low, and use value is high, and use range is extensive；By using compatible
Agent, the interfacial tension between each raw material is reduced, improve the interface cohesive force between each raw material, improve PP/COC alloy materials
Expect the compatible role of material；By using toughener, the toughness of PP/COC alloy materials, intensity, wearability, impact resistance are improved
The performances such as property；By using dispersant, the fully dispersed mixing of each raw material of PP/COC alloy materials can be made, and then play each raw material
Maximum performance effect, make obtained PP/COC alloy materials have preferable toughness, corrosion resistance, wearability, oil resistivity and
The performances such as impact resistance；By using lubricant, internal lubrication and external lubrication are played a part of to PP/COC alloy materials, carried
The high processability and processing characteristics of PP/COC alloy materials；By using antioxidant, PP/COC alloys can be effectively reduced
The thermal-oxidative degradation degree of material, preferable mechanical property can be kept for a long time.
Above-described embodiment is the preferable implementation of the present invention, and in addition, the present invention can be realized with other manner,
Do not depart from and any on the premise of present inventive concept obviously replace within protection scope of the present invention.
Claims (10)
- A kind of 1. PP/COC alloy materials of high intensity, low-shrinkage, it is characterised in that：The alloy material includes following parts by weight Raw material：Polypropylene 20-80 partsCyclic olefine copolymer 20-50 partsCompatilizer 1-5 partsToughener 1-5 partsDispersant 0.1-0.5 partsLubricant 0.2-0.8 partsAntioxidant 0.1-0.3 parts.
- 2. the PP/COC alloy materials of a kind of high intensity according to claim 1, low-shrinkage, it is characterised in that：It is described Cyclic olefine copolymer be molecular weight 4000-50000, the degree of polymerization 200-800 amorphism cyclic olefine copolymer.
- 3. the PP/COC alloy materials of a kind of high intensity according to claim 1, low-shrinkage, it is characterised in that：It is described Compatilizer is cyclic acid anhydride type compatilizer, carboxylic acid type compatilizer, epoxide resin type compatilizer, oxazoline type compatilizer, acid imide At least one of type compatilizer and isocyanate-based compatilizer.
- 4. the PP/COC alloy materials of a kind of high intensity according to claim 3, low-shrinkage, it is characterised in that：It is described Cyclic acid anhydride type compatilizer is maleic anhydride stem grafting polyolefin, and the carboxylic acid type compatilizer is that ethylene-acrylic acid esters ternary is gathered Compound is grafted ethylene oxidic ester, and the oxazoline type compatilizer is oxazoline grafted polystyrene, and the acid amide type compatilizer is Sub- amide modifications acrylate, the isocyanate-based compatilizer are m- isopropenyl -2,2- dimethyl benzoyl isocyanates.
- 5. the PP/COC alloy materials of a kind of high intensity according to claim 1, low-shrinkage, it is characterised in that：It is described Toughener be methyl methacrylate-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, Haloflex, ethylene-vinyl acetate copolymer, polyvinyl butyral resin, styrene butadiene thermoplasticelastomer and poly- At least one of acid imide.
- 6. the PP/COC alloy materials of a kind of high intensity according to claim 1, low-shrinkage, it is characterised in that：It is described Dispersant is carmethose, polyoxypropylene, polyoxyethylene copolymer, alkyl polyoxyethylene, polyethenoxy ether, dodecyl At least one of benzene sulfonic acid sodium salt, Sodium Polyacrylate, sodium polymethacrylate, sulfonated polyaniline and sodium taurocholate.
- 7. the PP/COC alloy materials of a kind of high intensity according to claim 1, low-shrinkage, it is characterised in that：It is described Lubricant is stearic amide, N, N '-ethylenebisstearamide, n-butyl stearate, the hydroxy stearic acid ester of glycerine three, polyethylene At least one of wax, polymethylphenyl siloxane fluid, ethylene bis stearamide and zinc stearate.
- 8. the PP/COC alloy materials of a kind of high intensity according to claim 1, low-shrinkage, it is characterised in that：It is described Antioxidant is the double -3- of triethylene glycol（3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls）Acrylate, N, N '-hexamethylene bis（3, 5- di-t-butyl -4- hydroxyl hydrocinnamamides）, 1,3,5-three (3,5 di-tert-butyl-hydroxy phenyl) isocyanates, three (2,4- Di-tert-butyl-phenyl) phosphite ester, 1,3,5- tri-（3,5 tertiary butyl-4-hydroxy benzyls）Trimethylbenzene, β（3,5 di-t-butyls- 4-hydroxy phenyl) at least one of propionic acid octadecyl and 2,6 BHTs.
- 9. a kind of preparation method of the PP/COC alloy materials of high intensity, low-shrinkage as described in claim 1-8, its feature It is：Comprise the following steps：Raw material is weighed according to parts by weight, and is mixed, then extruded equipment is melted, squeezed Go out, be granulated, obtain high intensity, the PP/COC alloy materials of low-shrinkage.
- 10. the preparation method of the PP/COC alloy materials of a kind of high intensity according to claim 9, low-shrinkage, it is special Sign is：The mixing rotating speed of the mixing is 400-800r/min, incorporation time 3-5min；The one of the extrusion equipment Area's temperature is 260-270 DEG C, and two area's temperature are 265-275 DEG C, and three area's temperature are 275-285 DEG C, and four area's temperature are 275-285 DEG C, five area's temperature are 275-285 DEG C, and six area's temperature are 270-280 DEG C.
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| CN109721828A (en) * | 2018-11-23 | 2019-05-07 | 金旸（厦门）新材料科技有限公司 | A kind of high heat resistance and cold-resistant high-gloss metal texture are exempted to spray PP material and preparation method thereof |
| CN109777025A (en) * | 2018-12-25 | 2019-05-21 | 浙江普利特新材料有限公司 | A kind of high rigidity, high tenacity, low-shrink polypropylene composite material and preparation method |
| CN109776965A (en) * | 2019-01-30 | 2019-05-21 | 江苏金发科技新材料有限公司 | Heat resistant polypropylene nanocomposite and preparation method thereof |
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