CN105504512A - Shallow-sink-mark reinforced polypropylene material and preparing method thereof - Google Patents

Shallow-sink-mark reinforced polypropylene material and preparing method thereof Download PDF

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Publication number
CN105504512A
CN105504512A CN201610003681.6A CN201610003681A CN105504512A CN 105504512 A CN105504512 A CN 105504512A CN 201610003681 A CN201610003681 A CN 201610003681A CN 105504512 A CN105504512 A CN 105504512A
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China
Prior art keywords
polypropylene material
reinforced polypropylene
shrink mark
shallow
mark
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CN201610003681.6A
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Chinese (zh)
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CN105504512B (en
Inventor
汪理文
董骏
周明
翁永华
丁贤麟
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Suzhou Runjia Polymer Materials Co ltd
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SUZHOU RUNJIA ENGINEER PLASTIC CO Ltd
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

The invention discloses a shallow-sink-mark reinforced polypropylene material and a preparing method thereof. The shallow-sink-mark reinforced polypropylene material is prepared from, by mass, 50%-70% of polypropylene, 5%-20% of nylon resin, 1%-5% of maleic-anhydride-grafted POE, 1%-5% of compatilizer, 5%-15% of K resin, 15%-25% of expansion microballoons and 1%-3% of organic clay. The surface of the product is high in quality, smooth, flat and resistant to sink marks and scratching, the product is high in strength, and application to appearance products such as domestic appliances and automobiles with higher appearance requirements can be achieved.

Description

A kind of shallow shrink mark Reinforced Polypropylene material and preparation method thereof
Technical field
The present invention relates to a kind of shallow shrink mark Reinforced Polypropylene material and preparation method thereof.
Background technology
Acrylic resin is as a kind of environmentally friendly material, and its use range expands rapidly.But due to polypropylene material, cooling curing speed is slow after moulding, the position of variation in thickness is there is in product, easily there is shrink mark phenomenon, shrink mark refers to the local dent formed at article surface, shrink mark often produces in the larger region of local wall thickness, the back side of muscle or thrust, does not obtain enough compensation produce by product thick wall part when cooling.This surface imperfection has a strong impact on the appearance looks elegant degree of goods, and still visible after spray coating, strongly limit the use of polypropylene material in appearance part.
Research shows, the formation of shrink mark is except outside the Pass having with product design, die design, moulding process etc., also there are much relations with material itself, first, crystalline material more easily produces shrink mark for amorphous material, because crystalline material is from molten state to the process of room temperature, molecular chain ordered arrangement forms crystal.Polypropylene material belongs to crystalline material, and shrinking percentage own is large, so be easy to produce shrink mark, secondly, the viscosity of material and filling additive etc. should also have very large impact to the product of shrink mark.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of shallow shrink mark Reinforced Polypropylene material and preparation method thereof.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A kind of shallow shrink mark Reinforced Polypropylene material, is prepared from by the raw material of following component, each component by mass percentage: polypropylene 50-70%, nylon resin 5-20%, maleic anhydride graft POE1-5%, compatilizer 1-5%, K resin 5-15%, expandable microspheres 15-25, polyorganosilicate 1-3%.
Namely K resin refers to transparent butadiene-styrene impact resin.
Described expandable microspheres shell is acrylic copolymer, and the whipping agent of interior bag is iso-pentane, and described expandable microspheres median size is 25-35 μm.
Described polyorganosilicate is organic ammonium modification smectite polyorganosilicate.
Described nylon resin is the semicrystalline polyamides of aliphatic dicarboxylic acid and the aliphatie diamine condensation comprising 4 to 12 carbon atoms.
Described polypropylene be under temperature 230 DEG C of load 2.16Kg melting index in the homo-polypropylene of 25-50g/10min.
Described compatilizer be selected from polypropylene grafted maleic anhydride, styrene-grafted maleic anhydride, grafting maleic anhydride with ethylene propylene terpolymer and terpolymer EP rubber graft glycidyl methacrylate one or more.
A preparation method for above-mentioned shallow shrink mark Reinforced Polypropylene material, comprises step:
(1) each component is fallen in super mixer by proportioning stir, through forcing machine extruding pelletization, obtain plastic master batch;
(2) by step (1) to plastic master batch add injection moulding in injection moulding machine, obtain desired product.
The beneficial effect that the present invention reaches:
(1) product surface quality of the present invention is high, not only smooth, nonshrink trace, and scratch resistant, and the intensity of goods is higher, can meet the application to the higher looking products such as household electrical appliance, automobile of appearance requirement;
(2) nylon, particularly aliphatic dicarboxylic acid can provide splendid mechanical property with the semicrystalline polyamides of the aliphatie diamine condensation that comprises 4 to 12 carbon atoms, with polypropylene with the use of the collection of material obtained both advantages;
(3) expandable microspheres plays internal expansion effect in whole blended system, can effectively offset the volumetric shrinkage caused because of crystalling propylene, thus ensure the dimensional stability of goods, the generation of opposing shrink mark, the viscosity of polyorganosilicate regulation system, suitable viscosity enough reduces punch die resistance, improves pressurize feeding effect, improve the shrink mark of product, improve products surface quality.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.Following examples only for technical scheme of the present invention is clearly described, and can not limit the scope of the invention with this.
Embodiment 1-3
The each component of embodiment 1-3 and mass percent proportioning are see table 1, and preparation method comprises step: each component is fallen in super mixer by proportioning and stirred by (1), through forcing machine extruding pelletization, obtains plastic master batch; (2) by step (1) to plastic master batch add injection moulding in injection moulding machine, obtain desired product.
Wherein, in embodiment 1-3 polypropylene used be under temperature 230 DEG C of load 2.16Kg melting index in the homo-polypropylene of 25-50g/10min.Nylon resin is the semicrystalline polyamides of aliphatic dicarboxylic acid and the aliphatie diamine condensation comprising 4 to 12 carbon atoms.Polyorganosilicate is organic ammonium modification smectite polyorganosilicate, and expandable microspheres shell is acrylic copolymer, and the whipping agent of interior bag is iso-pentane, and expandable microspheres median size is 30 μm.Compatilizer is nonrecoverable is polypropylene grafted maleic anhydride, styrene-grafted maleic anhydride, the mixture of styrene-grafted maleic anhydride and grafting maleic anhydride with ethylene propylene terpolymer.
Comparative example 1-3
Comparative example 1-3 feed components formula is see table 1, the all logical embodiment 2 of each method for preparing ingredients thereof, wherein, comparative example 1 is do not use nylon resin in filling a prescription with the difference of embodiment 2, comparative example 2 is do not use expandable microspheres in filling a prescription with the difference of embodiment 2, and comparative example 3 is do not use polyorganosilicate in filling a prescription with the difference of embodiment 2.
Each component formula in table 1 embodiment and comparative example:
。
Performance test
Performance test comprise measuring mechanical property and appearance test, the test result of embodiment 1-3 and comparative example 1-3 in table 2, wherein:
Measuring mechanical property standard measures tensile modulus according to ISO527-2/1B/1, and appearance property test uses injection moulding sample (melt temperature: about 290 DEG C; Die temperature: about 90 DEG C, and dwell pressure is 90MPa), carry out appearance and shrink mark measurement.In the mould with smooth surface (namely without texture), molding has the test sample book of 353 × 100 × 2mm rectangular shape.Test sample book has the rib of 25 × 5 × 1.5mm.The test sample book of molding dry state (DAM) is measured at 23 DEG C.Shrink mark degree of depth step instrument is measured, surfacing, the outward appearance visual method such as smooth.Scratch resistant performance adopts the evaluation of damage resistant tester, with one, mechanically operated scraper is scraped a line segment figure on the frosting of preparation.Then the misalignment of non-surface scratch is recorded with a colourimeter.In same sample region, scratch front and rear surfaces scattering of light value by spectral photometric colour measuring other measure sample of scoring, to scratch the quality of front and back scattering of light difference DELTA E tolerance studies on scratch resistance of PP, Δ E value is less, shows that the scratch resistance of goods is better.
Table 2 embodiment and comparative example the performance test results:
。
As seen from Table 2, the Effect on Mechanical Properties of nylon to material monolithic is larger, expandable microspheres and polyorganosilicate for raising products surface quality and nonshrink trace performance contribution larger, the polypropylene material of the present invention not only strength of materials is high, scratch resistant performance is excellent, and the nonshrink trace situation of product surface and visual appearance can reach and balance well.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvement and distortion, these improve and distortion also should be considered as protection scope of the present invention.

Claims (7)

1. a shallow shrink mark Reinforced Polypropylene material, it is characterized in that, be prepared from by the raw material of following component, each component is by mass percentage: polypropylene 50-70%, nylon resin 5-20%, maleic anhydride graft POE1-5%, compatilizer 1-5%, K resin 5-15%, expandable microspheres 15-25%, polyorganosilicate 1-3%.
2. one according to claim 1 shallow shrink mark Reinforced Polypropylene material, is characterized in that, described expandable microspheres shell is acrylic copolymer, and the whipping agent of interior bag is iso-pentane, and described expandable microspheres median size is 25-35 μm.
3. one according to claim 1 and 2 shallow shrink mark Reinforced Polypropylene material, is characterized in that, described polyorganosilicate is organic ammonium modification smectite polyorganosilicate.
4. one according to claim 3 shallow shrink mark Reinforced Polypropylene material, is characterized in that, described nylon resin is the semicrystalline polyamides of aliphatic dicarboxylic acid and the aliphatie diamine condensation comprising 4 to 12 carbon atoms.
5. one according to claim 1 shallow shrink mark Reinforced Polypropylene material, is characterized in that, described polypropylene be under temperature 230 DEG C of load 2.16Kg melting index in the homo-polypropylene of 25-50g/10min.
6. one according to claim 1 shallow shrink mark Reinforced Polypropylene material, it is characterized in that, described compatilizer be selected from polypropylene grafted maleic anhydride, styrene-grafted maleic anhydride, grafting maleic anhydride with ethylene propylene terpolymer and terpolymer EP rubber graft glycidyl methacrylate one or more.
7. the shallow shrink mark Reinforced Polypropylene material preparation method as described in any one of claim 1-6, is characterized in that, comprise step:
(1) each component is added in super mixer by proportioning stir, through forcing machine extruding pelletization, obtain plastic master batch;
(2) by step (1) to plastic master batch add injection moulding in injection moulding machine, obtain desired product.
CN201610003681.6A 2016-01-05 2016-01-05 A kind of shallow shrink mark RPP material and preparation method thereof Active CN105504512B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107987453A (en) * 2017-12-15 2018-05-04 会通新材料股份有限公司 One kind injection grade polypropylene/polyamide micro foaming composite material and preparation method thereof
CN110607004A (en) * 2019-09-20 2019-12-24 南京元初科技有限公司 Environment-friendly composite plastic with pearlescent effect and preparation method thereof
CN110982174A (en) * 2019-11-29 2020-04-10 苏州润佳高分子材料有限公司 Shallow sink mark reinforced polypropylene material for automobile
CN111087684A (en) * 2019-12-17 2020-05-01 会通新材料股份有限公司 Polypropylene-nylon 6 alloy micro-foaming wave-absorbing material and preparation method thereof
CN112480399A (en) * 2020-11-26 2021-03-12 贵州凯科特材料有限公司 Nucleating agent, composition for preparing transparent toughened nylon material, transparent toughened nylon material and preparation method thereof

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CN102382435A (en) * 2010-08-30 2012-03-21 陈金福 Biomass composite component and foaming method thereof
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107987453A (en) * 2017-12-15 2018-05-04 会通新材料股份有限公司 One kind injection grade polypropylene/polyamide micro foaming composite material and preparation method thereof
CN110607004A (en) * 2019-09-20 2019-12-24 南京元初科技有限公司 Environment-friendly composite plastic with pearlescent effect and preparation method thereof
CN110982174A (en) * 2019-11-29 2020-04-10 苏州润佳高分子材料有限公司 Shallow sink mark reinforced polypropylene material for automobile
CN111087684A (en) * 2019-12-17 2020-05-01 会通新材料股份有限公司 Polypropylene-nylon 6 alloy micro-foaming wave-absorbing material and preparation method thereof
CN112480399A (en) * 2020-11-26 2021-03-12 贵州凯科特材料有限公司 Nucleating agent, composition for preparing transparent toughened nylon material, transparent toughened nylon material and preparation method thereof

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Effective date of registration: 20191213

Address after: No.91, Qinan Road, Xiangcheng District, Suzhou City, Jiangsu Province

Patentee after: Suzhou Runjia polymer materials Co.,Ltd.

Address before: 698 No. 215122 Jiangsu Province, Suzhou City Industrial Park Fengting Avenue

Patentee before: SUZHOU RUNJIA ENGINEER PLASTIC Co.,Ltd.

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Denomination of invention: A shallow shrinkage mark reinforced polypropylene material and its preparation method

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