CN109467819A - Low warp glass fiber reinforced polypropylene compound material and preparation method thereof - Google Patents
Low warp glass fiber reinforced polypropylene compound material and preparation method thereof Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/14—Copolymers of propene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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Abstract
The invention proposes a kind of low warp glass fiber reinforced polypropylene compound materials and preparation method thereof, including following components: 55~65 parts of acrylic resin, 10~15 parts of alkali-free glass fibre, 20~30 parts of organics coating modification carborundum powder, 8~12 parts of four-needle-shape nano zinc oxide whisker, 2~4 parts of dimethyl itaconate, 1~3 part of titanate coupling agent, 6~12 parts of toughener, 0.5~1.2 part of heat stabilizer, 0.2~0.8 part of antioxidant and 0.6~1.8 part of lubricant.Preparation method: acrylic resin, the alkali-free glass fibre for accounting for gross mass 30~40%, titanate coupling agent, toughener, heat stabilizer, antioxidant and lubricant are added twin-screw extrude at mouth by main feed, organics coating modification carborundum powder, dimethyl itaconate and remaining alkali-free glass fibre add twin-screw extrude from side feed mouth, melting extrusion is granulated, and extrusion temperature is 200 DEG C~240 DEG C.The composite material has preferable low warpage properties and crocking resistance.
Description
Technical field
The invention belongs to plastics arts, and in particular to a kind of low warp glass fiber reinforced polypropylene compound material and its system
Preparation Method.
Background technique
Polypropylene enters each corner of daily life as a kind of general-purpose plastics, by the modified polypropylene of miberal powder
Material relies on its good rigidity, lower shrinking percentage and deformation, has obtained extensive utilization on household appliances.It is currently used
More methods is that elastomeric material is added in polypropylene matrix to improve impact strength, by introducing 10-40% talcum powder, cloud
The fillers such as female powder, wollastonite, kaolin improve tensile strength, bending strength and bending modulus, by introducing damage resistant agent such as
Silicone master batch, amide containing resinoid improve scratch resistant performance.
Polypropylene is one of five big general-purpose plastics, has excellent performance, is widely used to daily necessity, automobile, family
The fields such as electricity rely on its good rigidity by the modified polypropylene material of glass fibre, instead of engineering in certain applications
Plastics.But due to the difference of transverse and longitudinal shrinking percentage, cause fiber glass reinforced polypropylene material warpage serious.There are some patents to be directed to stick up
Song does certain improvement, but ineffective, and the effect in terms of thermal weld leakproofness and compressive resistance is also not so good as people's will.For
The polyacrylic rigidity of raising, heat resistance etc. are improved often through addition inorganic filler etc., and glass fibre is a kind of needle
Shape filler, to the performance of reinforced polypropylene in terms of tensile yield strength, flexural modulus, cantilever-type impact strength and heat resistance
There is larger impact.But usually with the increase for the glass fibre amount filled in acrylic resin, high-orientation makes molding
Product generate very big difference between flow direction and contraction rate perpendicular to flow direction, so that causing sticking up for final product
Song makes it in the revolving part such as fan for needing high-dimensional stability, interior bucket, impeller, is difficult to obtain using in big ruler in belt pulley
Degree product in be easy to happen big warpage and deformation, in addition glass fibre is easy to be exposed to product surface, cause surface property compared with
Difference, appearance is poor, meanwhile, when in composition have compared with high filler content such as more than 35wt% when, processing becomes difficult, and reduces
Production efficiency and processing performance.
Summary of the invention
The present invention proposes a kind of low warp glass fiber reinforced polypropylene compound material, which has preferable low warpage
Property and crocking resistance.
The technical scheme of the present invention is realized as follows:
A kind of low warp glass fiber reinforced polypropylene compound material, according to the number of parts by weight, including following components:
55~65 parts of acrylic resin, 10~15 parts of alkali-free glass fibre, 20~30 parts of organics coating modification carborundum powder,
8~12 parts of four-needle-shape nano zinc oxide whisker, 2~4 parts of dimethyl itaconate, 1~3 part of titanate coupling agent, toughener 6~12
Part, 0.5~1.2 part of heat stabilizer, 0.2~0.8 part of antioxidant and 0.6~1.8 part of lubricant.
Preferably, the organics coating modification carborundum powder first passes through surface again after silane coupling agent processing by silicon carbide
Graft acrylamide obtains.
Preferably, the titanate coupling agent is (the dioctyl phosphoric acid acyloxy) titanate esters of isopropyl three or three different hard esters
Sour isopropyl titanate.
Preferably, the acrylic resin is one or both of copolymer polypropylene or homopolypropylene.
Preferably, the heat stabilizer is selected from one of sub- phenolic thermostabilizers, phosphite ester type thermal stabilizing agent or more
Kind.
Preferably, the toughener is ethylene-octene copolymer, ethylene-alpha-olefin polymers or Ethylene-Propylene-Diene
One of copolymer or more than one.
Preferably, the antioxidant is selected from four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, Asia
One of tricresyl phosphate (2,4- di-tert-butyl-phenyl) ester and the double octadecyls of thio-2 acid are a variety of.
Preferably, the lubricant is zinc stearate or polypropylene wax.
It is a further object to provide a kind of preparation method of low warp glass fiber reinforced polypropylene compound material, packets
Include following steps:
Acrylic resin, the alkali-free glass fibre for accounting for gross mass 30~40%, titanate coupling agent, toughener, heat is steady
Determine agent, antioxidant and lubricant to add twin-screw extrude at mouth by main feed, organics coating modification carborundum powder, itaconic acid
Dimethyl ester and remaining alkali-free glass fibre add twin-screw extrude from side feed mouth, and melting extrusion is granulated, and extrusion temperature is
200 DEG C~240 DEG C.
Beneficial effects of the present invention:
Of the invention is added to poly- third by selection organics coating modification carborundum powder and four-needle-shape nano zinc oxide whisker
In alkene matrix resin, it is aided with dimethyl itaconate (as nucleating agent and promoting whisker dispersion), is compounded by each component, so that system
The difference of the shrinking percentage laterally and longitudinally of standby low warp glass fiber reinforced polypropylene compound material is very significantly improved, from root
The warpage properties of material are improved in sheet.In addition, dimethyl itaconate and the effect of four-needle-shape nano zinc oxide whisker improve poly- third
The crystallinity of alkene, to improve the mechanical property and scratch-resistant performance of material.
It is in preparation method of the invention that organics coating modification carborundum powder, dimethyl itaconate and remaining alkali-free glass is fine
Dimension promotes the low warpage properties energy and surface smoothness of material by the way of surveying feeding.
Specific embodiment
Embodiment 1
A kind of low warp glass fiber reinforced polypropylene compound material, according to the number of parts by weight, including following components:
61 parts of copolymer polypropylene, 12 parts of alkali-free glass fibre, 25 parts of organics coating modification carborundum powder, four-acicular nanometer oxygen
It is total to change 10 parts of zinc whisker, 3 parts of dimethyl itaconate, isopropyl three (dioctyl phosphoric acid acyloxy) 2 parts of titanate esters, ethylene-octene
9 parts of polymers, sub- 0.9 part of phenolic thermostabilizers, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters 0.5
Part and 0.9 part of zinc stearate.Organics coating modification carborundum powder first passes through surface again after silane coupling agent processing by silicon carbide
Graft acrylamide obtains.
Preparation method:
By copolymer polypropylene, the alkali-free glass fibre for accounting for gross mass 36%, isopropyl three (dioctyl phosphoric acid acyloxy) titanium
Acid esters, ethylene-octene copolymer, sub- phenolic thermostabilizers, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] Ji Wusi
Alcohol ester and zinc stearate are added twin-screw extrude at mouth by main feed, organics coating modification carborundum powder, itaconic acid diformazan
Ester and remaining alkali-free glass fibre add twin-screw extrude from side feed mouth, and melting extrusion is granulated, and extrusion temperature is 200 DEG C
~240 DEG C.
Embodiment 2
A kind of low warp glass fiber reinforced polypropylene compound material, according to the number of parts by weight, including following components:
55 parts of copolymer polypropylene, 15 parts of alkali-free glass fibre, 20 parts of organics coating modification carborundum powder, four-acicular nanometer oxygen
It is total to change 12 parts of zinc whisker, 2 parts of dimethyl itaconate, isopropyl three (dioctyl phosphoric acid acyloxy) 1 part of titanate esters, ethylene-octene
6 parts of polymers, sub- 0.5 part of phenolic thermostabilizers, 0.2 part and 0.6 part of zinc stearate of phosphorous acid three (2,4- di-tert-butyl-phenyl) ester.
Organics coating modification carborundum powder by silicon carbide first pass through silane coupling agent processing after again surface grafting acrylamide obtain.
Preparation method:
By copolymer polypropylene, the alkali-free glass fibre for accounting for gross mass 30%, isopropyl three (dioctyl phosphoric acid acyloxy) titanium
Acid esters, ethylene-octene copolymer, sub- phenolic thermostabilizers, (2, the 4- di-tert-butyl-phenyl) ester of phosphorous acid three and zinc stearate are logical
It crosses main feed to add twin-screw extrude at mouth, organics coating modification carborundum powder, dimethyl itaconate and remaining alkali-free glass
Fiber adds twin-screw extrude from side feed mouth, and melting extrusion is granulated, and extrusion temperature is 200 DEG C~240 DEG C.
Embodiment 3
A kind of low warp glass fiber reinforced polypropylene compound material, according to the number of parts by weight, including following components:
65 parts of homopolypropylene, 10 parts of alkali-free glass fibre, 30 parts of organics coating modification carborundum powder, four-acicular nanometer oxygen
Change 8 parts of zinc whisker, 4 parts of dimethyl itaconate, 3 parts of three iso stearate isopropyl titanate, 12 parts of ethylene-propylene-diene copolymer,
1.2 parts of phosphite ester type thermal stabilizing agent, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] 0.8 part of pentaerythritol esters and
1.8 parts of polypropylene wax.Organics coating modification carborundum powder first passes through surface grafting again after silane coupling agent processing by silicon carbide
Acrylamide obtains.
Preparation method:
By homopolypropylene, the alkali-free glass fibre for accounting for gross mass 40%, three iso stearate isopropyl titanates, ethylene-the third
Alkene-diene copolymers, phosphite ester type thermal stabilizing agent, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythrites
Ester and polypropylene wax are added twin-screw extrude at mouth by main feed, organics coating modification carborundum powder, dimethyl itaconate
Added twin-screw extrude from side feed mouth with remaining alkali-free glass fibre, melting extrusion be granulated, extrusion temperature be 200 DEG C~
240℃。
Comparative example 1
A kind of low warp glass fiber reinforced polypropylene compound material, it is substantially the same manner as Example 1, do not contain organics coating modification
Carborundum powder, four-needle-shape nano zinc oxide whisker and dimethyl itaconate.
Comparative example 2
A kind of low warp glass fiber reinforced polypropylene compound material, it is substantially the same manner as Example 1, do not contain four-acicular nanometer oxygen
Change zinc whisker.
Test example
Examples 1 to 3, the low warp glass fiber reinforced polypropylene compound material of comparative example 1~2 are tested for the property, stuck up
Song test: sample is molded into the square plate of 100*100*1mm, observes template flatness after cooling.Skin-friction coefficient test
Standard foundation ISO8295, test condition: 23 DEG C of temperature, sample thickness 0.5mm.Measurement result is shown in Table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | |
| Angularity (mm) | 0.93 | 1.02 | 0.88 | 2.05 | 1.54 |
| Coefficient of friction | 0.19 | 0.23 | 0.16 | 0.21 | 0.38 |
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of low warp glass fiber reinforced polypropylene compound material, which is characterized in that according to the number of parts by weight, including with the following group
Point:
55~65 parts of acrylic resin, 10~15 parts of alkali-free glass fibre, 20~30 parts of organics coating modification carborundum powder, four needles
8~12 parts of shape nano zinc oxide crystal whisker, 2~4 parts of dimethyl itaconate, 1~3 part of titanate coupling agent, 6~12 parts of toughener,
0.5~1.2 part of heat stabilizer, 0.2~0.8 part of antioxidant and 0.6~1.8 part of lubricant.
2. low warp glass fiber reinforced polypropylene compound material according to claim 1, which is characterized in that the organic coating
Modified silicon carbide by silicon carbide first pass through silane coupling agent processing after again surface grafting acrylamide obtain.
3. low warp glass fiber reinforced polypropylene compound material according to claim 1, which is characterized in that the titanate esters are even
Connection agent is (the dioctyl phosphoric acid acyloxy) titanate esters of isopropyl three or three iso stearate isopropyl titanates.
4. low warp glass fiber reinforced polypropylene compound material according to claim 1, which is characterized in that the polypropylene tree
Rouge is one or both of copolymer polypropylene or homopolypropylene.
5. low warp glass fiber reinforced polypropylene compound material according to claim 1, which is characterized in that the heat stabilizer
Selected from one of sub- phenolic thermostabilizers, phosphite ester type thermal stabilizing agent or a variety of.
6. low warp glass fiber reinforced polypropylene compound material according to claim 1, which is characterized in that the toughener is
One of ethylene-octene copolymer, ethylene-alpha-olefin polymers or ethylene-propylene-diene copolymer or more than one.
7. low warp glass fiber reinforced polypropylene compound material according to claim 1, which is characterized in that the antioxidant choosing
From four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, phosphorous acid three (2,4- di-tert-butyl-phenyl) ester
With one of double octadecyls of thio-2 acid or a variety of.
8. low warp glass fiber reinforced polypropylene compound material according to claim 1, which is characterized in that the lubricant is
Zinc stearate or polypropylene wax.
9. the preparation method of the low warp glass fiber reinforced polypropylene compound material as described in claim 1 to 8 any one, special
Sign is, comprising the following steps:
By acrylic resin, the alkali-free glass fibre for accounting for gross mass 30~40%, titanate coupling agent, toughener, heat stabilizer,
Antioxidant and lubricant are added twin-screw extrude at mouth by main feed, organics coating modification carborundum powder, itaconic acid diformazan
Ester and remaining alkali-free glass fibre add twin-screw extrude from side feed mouth, and melting extrusion is granulated, and extrusion temperature is 200 DEG C
~240 DEG C.
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| CN201811211381.2A CN109467819A (en) | 2018-10-17 | 2018-10-17 | Low warp glass fiber reinforced polypropylene compound material and preparation method thereof |
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| CN201811211381.2A CN109467819A (en) | 2018-10-17 | 2018-10-17 | Low warp glass fiber reinforced polypropylene compound material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110885495A (en) * | 2019-12-13 | 2020-03-17 | 天津金发新材料有限公司 | Low-emission low-warpage glass fiber reinforced polypropylene composite material and preparation method thereof |
| CN111073146A (en) * | 2019-12-26 | 2020-04-28 | 苏州润佳高分子材料有限公司 | Polypropylene-ethylene propylene diene monomer modified composite material for automobile |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110885495A (en) * | 2019-12-13 | 2020-03-17 | 天津金发新材料有限公司 | Low-emission low-warpage glass fiber reinforced polypropylene composite material and preparation method thereof |
| CN110885495B (en) * | 2019-12-13 | 2022-06-14 | 天津金发新材料有限公司 | Low-emission low-warpage glass fiber reinforced polypropylene composite material and preparation method thereof |
| CN111073146A (en) * | 2019-12-26 | 2020-04-28 | 苏州润佳高分子材料有限公司 | Polypropylene-ethylene propylene diene monomer modified composite material for automobile |
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Application publication date: 20190315 |