CN106279976B - Fretting map High-strength polypropylene composite material - Google Patents

Fretting map High-strength polypropylene composite material Download PDF

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Publication number
CN106279976B
CN106279976B CN201610654477.0A CN201610654477A CN106279976B CN 106279976 B CN106279976 B CN 106279976B CN 201610654477 A CN201610654477 A CN 201610654477A CN 106279976 B CN106279976 B CN 106279976B
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parts
polypropylene
composite material
fretting map
foaming agent
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CN106279976A (en
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汪理文
李庆贵
孙兆才
董骏
周明
翁永华
丁贤麟
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SUZHOU RUNJIA ENGINEER PLASTIC 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
    • C08J9/06—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 chemical blowing agent
    • C08J9/08—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 chemical blowing agent developing carbon dioxide
    • 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
    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/08—Copolymers of styrene
    • C08J2425/10—Copolymers of styrene with conjugated dienes
    • 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

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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)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of fretting map High-strength polypropylene composite materials, according to parts by weight, it is prepared by the raw material for including following components: 100 parts of polypropylene, 0.001-0.01 parts of organic peroxide, 10-15 parts of K resin, 1-5 parts of inorganic foaming agent of organic polymer cladding, 5-15 parts of talcum powder, 1-5 parts of auxiliary agent, the auxiliary agent includes surfactant, foaming stabiliser and thermal stabilizer, and the particle size of the talcum powder is 100-5000 mesh.Formula of the invention is raw materials used to be easy to get, at low cost, especially foaming agent NaHCO3, economic and environment-friendly, the automobile microporous foam polypropylene material that the closed pore of injection grade, distribution of cells are uniform, frothing percentage is high, physical and mechanical property is excellent can be made in cooperation other components.

Description

Fretting map High-strength polypropylene composite material
Technical field
The present invention relates to a kind of PP composite materials, and in particular to a kind of fretting map High-strength polypropylene composite material.
Background technique
Based on automobile industry development demand and state of development, it has been developed that polypropylene micro foaming injection moulding technology. This technology refers to using polypropylene material as matrix, by Shooting Technique, under the action of gas internal pressure, keeps product middle layer close Closed porosity of the cloth size from ten to tens micron and there are fine and close epidermal structure in two sides；Material and loss of weight are saved to reach Purpose.
Although the more unexpanded substantially reduced weight of solid material after the molding of fretting map PP foaming materials, condition of equivalent thickness material Rigidity, toughness but have corresponding decline.Simultaneously as material is molded material compared with conventional tubeless in unexpanded preceding Injection filling thickness Material wants much lower, therefore, requires the molding mobility of PP basic material also far beyond conventional tubeless injected plastics material.In addition, Although the material of overseas enterprise (such as Basel, Borealis etc.) is started to walk early, expensive, therefore, in addition to improve poly- third Outside the mobility of alkene composite material, mechanical property, in order to guarantee the competition of product, control cost is also needed.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the defects of the prior art, provide a kind of fretting map high-strength polypropylene Composite material, the polypropylene material have high fluidity, high-intensitive characteristic, can be realized loss of weight, life efficiently, inexpensive It produces.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
A kind of fretting map High-strength polypropylene composite material is prepared by the raw material for including following components according to parts by weight It forms: 100 parts of polypropylene, 0.001-0.01 parts of organic peroxide, 10-15 parts of K resin, the inorganic hair of organic polymer cladding 1-5 parts of infusion, 5-15 parts of talcum powder, 1-5 parts of auxiliary agent, the auxiliary agent includes surfactant, foaming stabiliser and thermal stabilizer, institute The particle size for stating talcum powder is 100-5000 mesh.
Preferably, foaming stabiliser is the foaming stabilizer of methyl glycol fatty acid ester class, and thermal stabilizer is for calcium stearate or firmly Resin acid barium.
Preferably, the polypropylene is homopolypropylene, and the polyacrylic isotacticity is greater than 97%, the polypropylene root According to ASTMD1238-99,230 DEG C/2.16kg of condition, the solution flow rate of measurement is 1-10g/10min.
Preferably, the inorganic foaming agent is NaHCO3, organic polymer cladding inorganic foaming agent in organic polymer For one of polyurethane-modified organic silicon resin, polyalkyl acrylate or poly- hydroxy acrylate or a variety of.
Preferably, the inorganic foaming agent of the organic polymer cladding is prepared by following methods: organic polymer is dissolved in After in organic solvent, NaHCO is added3Ultrasonic disperse is uniform, then stirs more than for 24 hours under 50-150r/min speed, with spin coating side Method drying, is dried in vacuo 0.2-1 hours, removes organic solvent, obtains the inorganic foaming agent of organic polymer cladding.
Preferably, the organic peroxide is selected from tert-butylperoxylaurate, t-butyl peroxybenzoate, tert-butyl mistake Oxygen isopropyl monocarbonate, cumyl peroxide, (benzoylperoxy) hexane of 2,5- dimethyl -2,5- bis- and 1,3- is bis- One of (t-butylperoxyisopropyl) benzene or a variety of mixtures.
Preferably, the surfactant is nonionic surfactant, and the nonionic surfactant is selected from second two Alcohol or glycerol pentaerythrite, the dosage of the nonionic surfactant are 0.01-0.1 parts.
Preferably, the fretting map High-strength polypropylene composite material has the following property:
According to ASTMD1238-99,230 DEG C/2.16kg of condition, solution flow rate >=40g/10min of measurement, abscess It 10-100 μm of diameter, according to fusing point >=152 DEG C that 3146 testing standard of DIN EN ISO measures, is measured according to ISO 180-A Notch impact strength >=35kJ/m2。
Preferably, formula of the invention before preparation, needs to add organic peroxide first by after polypropylene fusion Stirring then adds the preparation of remaining component.Shooting Technique well known in the art can be selected in preparation method.
Advantageous effects of the invention:
Formula of the invention is raw materials used to be easy to get, at low cost, especially foaming agent NaHCO3, it is economic and environment-friendly, cooperate other The automobile micropore hair that the closed pore of injection grade, distribution of cells are uniform, frothing percentage is high, physical and mechanical property is excellent can be made in component Foaming polypropylene material；
Organic peroxide not only improves polyacrylic melting tension, and the cooperation with other components also reduces rubber phase Viscosity, improve material flow fronts stability.K resin, that is, transparent butadiene-styrene impact resin, being capable of balancing material in component Toughness and rigidity, make material obtain comprehensive performance improve PP composite material.
Specific embodiment
The invention will be further described combined with specific embodiments below.Following embodiment is only used for clearly illustrating Technical solution of the present invention, and not intended to limit the protection scope of the present invention.
Embodiment 1
Weigh in parts by weight: 100 parts of polypropylene, 0.001 part of tert-butylperoxylaurate, 10 parts of K resin, polyurethane changes Property organic silicon resin cladding NaHCO32 parts of foaming agent, 5 parts of talcum powder, nonionic surfactant, methyl glycol fatty acid ester class Foaming stabilizer and totally 1 part of calcium stearate, the particle size of talcum powder is 1000 mesh.
First organic peroxide will be added after polypropylene fusion, then adds its in addition to foaming agent in component melts It is blended, obtains polypropylene-base, fretting map high-strength polypropylene then is made with Shooting Technique in the polypropylene-base and foaming agent Composite material, foamed material obtained are tested for the property, and test result is shown in Table 1.
Embodiment 2
It weighs in parts by weight: 100 parts of polypropylene, 2,5- dimethyl -2,5- bis- (benzoylperoxy) hexanes 0.006 Part, 12 parts of K resin, the NaHCO of polyalkyl acrylate cladding33 parts of foaming agent, 10 parts of talcum powder, ethylene glycol, propylene glycol fatty Totally 3 parts of the foaming stabilizer and barium stearate of esters of gallic acid, the particle size of talcum powder is 500 mesh.
First organic peroxide will be added after polypropylene fusion, then adds its in addition to foaming agent in component melts It is blended, obtains polypropylene-base, fretting map high-strength polypropylene then is made with Shooting Technique in the polypropylene-base and foaming agent Composite material, foamed material obtained are tested for the property, and test result is shown in Table 1.
Embodiment 3
It weighs in parts by weight: 100 parts of polypropylene, 0.003 part of tert-butylperoxyiso-propyl monocarbonate, 10 parts of K resin, The NaHCO of polyurethane-modified organic silicon resin cladding35 parts of foaming agent, 15 parts of talcum powder, glycerol pentaerythrite, propylene glycol fatty Totally 3 parts of the foaming stabilizer and calcium stearate of esters of gallic acid, the particle size of talcum powder is 3000 mesh.
First organic peroxide will be added after polypropylene fusion, then adds its in addition to foaming agent in component melts It is blended, obtains polypropylene-base, fretting map high-strength polypropylene then is made with Shooting Technique in the polypropylene-base and foaming agent Composite material, foamed material obtained are tested for the property, and test result is shown in Table 1.
Embodiment 4
Weigh in parts by weight: 100 parts of polypropylene, 0.001 part of tert-butylperoxylaurate, 10 parts of K resin, polyurethane changes Property organic silicon resin cladding NaHCO32 parts of foaming agent, 8 parts of talcum powder, the bubble of glycerol pentaerythrite, methyl glycol fatty acid ester class Hole stabilizer and totally 3 parts of calcium stearate, the particle size of talcum powder are 5000 mesh.
First organic peroxide will be added after polypropylene fusion, then adds its in addition to foaming agent in component melts It is blended, obtains polypropylene-base, fretting map high-strength polypropylene then is made with Shooting Technique in the polypropylene-base and foaming agent Composite material, foamed material obtained are tested for the property, and test result is shown in Table 1.
Comparative example 1
Weigh in parts by weight: 100 parts of polypropylene, 0.001 part of tert-butylperoxylaurate, 10 parts of K resin, polyurethane changes Property organic silicon resin cladding NaHCO32 parts of foaming agent, 5 parts of citric acid, 8 parts of talcum powder, glycerol pentaerythrite, propylene glycol fatty Totally 3 parts of the foaming stabilizer and calcium stearate of esters of gallic acid, the particle size of talcum powder is 5000 mesh.
First organic peroxide will be added after polypropylene fusion, then adds its in addition to foaming agent in component melts It is blended, obtains polypropylene-base, fretting map high-strength polypropylene then is made with Shooting Technique in the polypropylene-base and foaming agent Composite material, foamed material obtained are tested for the property, and test result is shown in Table 1.
Comparative example 2
It weighs in parts by weight: 100 parts of polypropylene, 0.001 part of tert-butylperoxylaurate, polyurethane-modified organosilicon tree The NaHCO of ester cladding32 parts of foaming agent, 8 parts of talcum powder, glycerol pentaerythrite, methyl glycol fatty acid ester class foaming stabilizer and Totally 3 parts of calcium stearate, the particle size of talcum powder is 5000 mesh.
First organic peroxide will be added after polypropylene fusion, then adds its in addition to foaming agent in component melts It is blended, obtains polypropylene-base, fretting map high-strength polypropylene then is made with Shooting Technique in the polypropylene-base and foaming agent Composite material, foamed material obtained are tested for the property, and test result is shown in Table 1.
Comparative example 3
Weigh in parts by weight: 100 parts of polypropylene, 0.001 part of tert-butylperoxylaurate, 10 parts of K resin, polyurethane changes Property organic silicon resin cladding NaHCO32 parts of foaming agent, 8 parts of talcum powder of polyurethane-modified organic silicon resin cladding, glycerol season Totally 3 parts of penta tetrol, the foaming stabilizer of methyl glycol fatty acid ester class and calcium stearate, the particle size of talcum powder is 5000 mesh.
First organic peroxide will be added after polypropylene fusion, then adds its in addition to foaming agent in component melts It is blended, obtains polypropylene-base, fretting map high-strength polypropylene then is made with Shooting Technique in the polypropylene-base and foaming agent Composite material, foamed material obtained are tested for the property, and test result is shown in Table 1.
Illustrate: polypropylene used is homopolypropylene in embodiment 1-4 and comparative example 1-3, and polyacrylic isotacticity Greater than 97%, the polypropylene is according to ASTMD1238-99, and 230 DEG C/2.16kg of condition, the solution flow rate of measurement is 1- 10g/10min。
Comparative example 4
Weigh in parts by weight: 100 parts of polypropylene, 0.001 part of tert-butylperoxylaurate, 10 parts of K resin, polyurethane changes Property organic silicon resin cladding NaHCO32 parts of foaming agent, 8 parts of talcum powder, the bubble of glycerol pentaerythrite, methyl glycol fatty acid ester class Hole stabilizer and totally 3 parts of calcium stearate, the particle size of talcum powder are 5000 mesh.
First organic peroxide will be added after polypropylene fusion, then adds its in addition to foaming agent in component melts It is blended, obtains polypropylene-base, fretting map high-strength polypropylene then is made with Shooting Technique in the polypropylene-base and foaming agent Composite material, foamed material obtained are tested for the property, and test result is shown in Table 1.
Polypropylene is copolymer polypropylene in this comparative example, and polypropylene is according to ASTMD1238-99,230 DEG C of condition/ 2.16kg, the solution flow rate of measurement are 20g/10min.
Performance test:
1. embodiment and comparative example the performance test results of table
The cell diameter of the PP composite material of embodiment 1-4 is 10-100 μm, and is the closed pore of injection grade, abscess It is evenly distributed, furthermore, do not occur the agglomeration of inorganic particle in embodiment 1-4, inorganic particle disperses good in resin matrix It is good.As seen from Table 1, present invention employs PP composite material made from raw material that is economic and environment-friendly, being easy to get obtain it is excellent Mechanical property and good appearance, do not lead to product appearance jaundice, peculiar smell because of addition peroxide in this formula etc. Problem reduces production cost, improves production efficiency.
It can be seen that by comparative example 1 and embodiment 4, be not added with lemon acid assistant, NaHCO is used only3Feelings as foaming agent Higher coefficient of foaming and excellent mechanical property are still obtained under condition, can be seen that by comparative example 3 and embodiment 4, in this formula, Organic polymer has been used to coat in the inorganic particle (talcum powder) and comparative example 3 coated using unused organic polymer inorganic Powder (talcum powder) obtains good result, does not reunite, appearance property is good.There are comparative example 4 and embodiment 4 that can see Out, the selection of pp material is affected to product comprehensive performance in formula.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, without departing from the technical principles of the invention, several improvement and deformations can also be made, these improvement and deformations Also it should be regarded as protection scope of the present invention.

Claims (4)

1. a kind of fretting map High-strength polypropylene composite material, which is characterized in that according to parts by weight, by including following components Raw material is prepared: 100 parts of polypropylene, 0 .003 parts of tert-butylperoxyiso-propyl monocarbonate, and 10-15 parts of K resin, You Jigao 1-5 parts of inorganic foaming agent of molecule cladding, 5-15 parts of talcum powder, 1-5 parts of auxiliary agent, the auxiliary agent includes surfactant, foaming Stabilizer and thermal stabilizer, the particle size of the talcum powder are 100-5000 mesh；The inorganic foaming agent is NaHCO3, You Jigao Organic polymer is polyurethane-modified organic siliconresin, polyalkyl acrylate or poly- hydroxyl in the inorganic foaming agent of molecule cladding One of base acrylate is a variety of.
2. a kind of fretting map High-strength polypropylene composite material according to claim 1, which is characterized in that the polypropylene For homopolypropylene, the polyacrylic isotacticity is greater than 97%, the polypropylene according to ASTMD1238-99,230 DEG C of condition/ 2 .16 kg, the solution flow rate of measurement are 1-10g/10min.
3. a kind of fretting map High-strength polypropylene composite material according to claim 1, which is characterized in that the surface is living Property agent be nonionic surfactant, the nonionic surfactant be selected from ethylene glycol or glycerol pentaerythrite, it is described it is non-from The dosage of sub- surfactant is .1 parts of 0 .01-0.
4. a kind of fretting map High-strength polypropylene composite material according to claim 1, which is characterized in that the fretting map High-strength polypropylene composite material has the following property: according to ASTMD1238-99,230 DEG C/2 .16 kg of condition, measurement Solution flow rate >=40g/10min, measures molten according to 3146 testing standard of DIN EN ISO by 10-100 μm of cell diameter Point >=152 DEG C, the notch impact strength measured according to ISO 180-A >=35 kJ/m2 。
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CN107522862A (en) * 2017-08-23 2017-12-29 成都新柯力化工科技有限公司 The polysiloxanes microballoon foaming agent and preparation method of a kind of expanded polypropylene plastics
CN110305412B (en) * 2019-07-22 2021-04-23 苏州润佳工程塑料股份有限公司 Chiral silica fiber reinforced foamed polypropylene composite material
CN111592703B (en) * 2020-05-18 2022-08-16 广德祥源新材科技有限公司 Environment-friendly cross-linked polyolefin foam material and preparation method thereof

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