CN105131432B - A kind of preparation method of automotive upholstery with environment protection modification polypropylene material - Google Patents
A kind of preparation method of automotive upholstery with environment protection modification polypropylene material Download PDFInfo
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- CN105131432B CN105131432B CN201510508794.7A CN201510508794A CN105131432B CN 105131432 B CN105131432 B CN 105131432B CN 201510508794 A CN201510508794 A CN 201510508794A CN 105131432 B CN105131432 B CN 105131432B
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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
- C08L23/14—Copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- 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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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of preparation method of automotive upholstery with environment protection modification polypropylene material, which comprises the steps：(1) monomer graft modification polypropylene is prepared, as compatilizer；(2) by 100 parts of acrylic resin, 4 10 parts of compatilizer, 0.1 0.5 parts of damage resistant agent, 0.1 0.5 parts of antistatic additive, 0.1 0.5 parts of age resister, 0.1 0.5 parts of flavouring are well mixed, stir in adding super mixer, control rotating speed is in 600 1000r/min, 90 120 DEG C of whipping temp, mixing time 10 20 minutes；(3) Jing screw extruders extruding pelletization, 200 220 DEG C of extrusion temperature, cooling again, obtains plastic grain；(4) plastic grain is added into injection mo(u)lding in injection machine, automotive upholstery environment protection modification polypropylene material is obtained.According to the automotive upholstery that the method for the present invention is prepared environment protection modification polypropylene material, intensity, bending strength, bending modulus and notch impact strength are drawn high with higher, antistatic property is good, and ageing resistace is good, free from extraneous odour.
Description
Technical field
The present invention relates to a kind of preparation method of plastics, more particularly to a kind of automotive upholstery environment protection modification polypropylene material
The preparation method of material.
Background technology
Acrylic resin (PP), is a kind of obtained thermoplastic resin by propylene polymerization.It is divided into by methyl arrangement position
Isotactic polypropylene (isotactic polyprolene), random polypropylene (atactic polypropylene) and a rule poly- third
Three kinds of alkene (syndiotactic polypropylene).
Methyl is arranged in the same side of molecular backbone and claims isotactic polypropylene, if the chaotic molecular backbone that is arranged in of methyl
Both sides claim random polypropylene, when the both sides that methyl is arranged alternately in molecular backbone claim syndiotactic polypropylene.It is poly- that general industry is produced
In allyl resin, isotactic structural content is about 95%, and remaining is random or syndiotactic polypropylene.Industrial products are main with isotactic thing
Composition.Including polypropylene copolymer also including propylene with a small amount of ethene.Usually translucent colorless solid, odorless are nontoxic.By
In compound with regular structure highly crystallized, therefore fusing point may be up to 167 DEG C.Heat-resisting, corrosion-resistant, product can be its protrusion with moise-heat sterilization
Advantage.Density is little, is most light general-purpose plastics.Have the disadvantage that low-temperature impact resistance is poor, be easier to aging, but can be given by modified respectively
To overcome.
With the development of society, people's living standard is increasingly improved, and automobile has been increasingly becoming a part for people's life.People
Requirement to automobile also more and more higher, do not require nothing more than automobile and there is good performance, and pursue automobile have it is good
Appearance profile and Comfortable attractive interior trim.
Automotive upholstery, is primarily referred to as the used automobile product of automotive interior repacking, is related to the Fang Fang of automotive interior
Face face, such as glove box, automobile seat backboard, automobile elbow-board, automobile side plate, column guard board, door-plate, fascia, vapour
Car auxiliary fasia console, undertray, case for radio and central control board etc. are all automotive upholstery products.Automotive trim system is automobile
The important component part of vehicle body, and the design efforts would of interior decoration system accounts for more than the 60% of car shape-designing workload, far
More than car conour, it is one of most important part of vehicle body.
Current polypropylene generally has poor, impact resistance difference of scratch resistant performance etc. to ask for the automotive upholstery of main material
Topic.
The content of the invention
A kind of automobile is provided for one of above-mentioned deficiency, the technical problem to be solved present in prior art
Preparation method of the inside gadget with environment protection modification polypropylene material.
The present invention seeks to be achieved through the following technical solutions：
A kind of preparation method of automotive upholstery with environment protection modification polypropylene material, which comprises the steps：
(1) monomer graft modification polypropylene is prepared, as compatilizer；
(2) by 100 parts of acrylic resin, compatilizer 4-10 parts, damage resistant agent 0.1-0.5 parts, antistatic additive 0.1-0.5
Part, age resister 0.1-0.5 parts, flavouring 0.1-0.5 parts are well mixed, and stir in adding super mixer, and control rotating speed exists
600-1000r/min, 90-120 DEG C of whipping temp, mixing time 10-20 minute；
(3) Jing screw extruders extruding pelletization, 200-220 DEG C of extrusion temperature, cooling again, obtains plastic grain；
(4) plastic grain is added into injection mo(u)lding in injection machine, automotive upholstery environment protection modification polypropylene is obtained
Material.
Preferably,
The polypropylene is COPP.
The monomer graft modification polypropylene is prepared as follows：
(1) 100 parts by weight of polypropylene, 1-15 weight parts monomers, 0.05-0.5 weight portion initiators are well mixed；
(2) 1-5min is heated at 170-220 DEG C, use granulator granulation.
Wherein,
The initiator is peroxide, such as cumyl peroxide (DCP) etc..
The polyacrylic percent grafting of the monomer graft modification is 0.5-10%, preferably 2-5%.
It is further preferred that
The compatilizer is 2- acrylamidos -3 Methylbutanoic acid graft modification polypropylene, methyl propenoic acid glycidyl
Ester graft modification polypropylene and 3- isopropenyls-alpha, alpha-dimethyl phenyl isocyanate graft modification polypropylene are according to mass ratio 1:
1:1 blending is formed.I.e. respectively with 2- acrylamidos -3 Methylbutanoic acid, GMA and 3- isopropenyls -
α, alpha-alpha-dimethyl phenyl isocyanate prepare monomer graft modification polypropylene as monomer, then according to mass ratio 1:1:1 blending
Form as compatilizer.
The damage resistant agent be -4 methoxy benzophenone of ricinoleic acid amide MEA, 2- hydroxyl, 2,2'- dihydroxy -4,
One kind or its mixture in 4'- dimethoxy-benzophenone -5,5'- sodium disulfonates.
Preferably, the damage resistant agent, is made up of by weight following components：Ricinoleic acid amide MEA10-30 parts, 2-
- 4 methoxy benzophenone 5-10 parts of hydroxyl, 2,2' dihydroxy 4,4' dimethoxy benzophenone -5,5'- sodium disulfonate 20-
40 parts.
The antistatic additive is selected from palmitamide hydroxypropyltrimonium chloride, N, double (2- the hydroxyethyls)-N- (3 '-ten of N-
Dialkoxy -2 '-hydroxypropyl) methylsulfuric acid ammonium methyl or stearamidopropyl dimethyl-beta-hydroxyethyl quaternary ammonium nitrate.
The age resister selected from the double dodecane ester of thio-2 acid, three (2,4- di-tert-butyl-phenyls) phosphite ester, two
Butylated hydroxytoluene or the double hydrazines of thio two propiono of N, N- diacetyl.
The flavouring is 3,5- di-t-butyl -4- hydroxycinnamic acids.
Obviously, other auxiliary agents are added to the property of may also adapt to improve other performances of product in the present invention, it is such as fire-retardant
Agent, colouring agent etc..
2- acrylamidos -3 Methylbutanoic acid, No. CAS：38486-53-5.
GMA, No. CAS：106-91-2.
3- isopropenyl-α, alpha-alpha-dimethyl phenyl isocyanate, No. CAS：2094-99-7.
- 4 methoxy benzophenone of 2- hydroxyls, No. CAS：131-57-7.
2,2'- dihydroxy -4,4'- dimethoxy-benzophenone -5,5'- sodium disulfonates, No. CAS：76656-36-5.
Palmitamide hydroxypropyltrimonium chloride, No. CAS：127311-98-2.
Ricinoleic acid amide MEA, No. CAS：106-16-1.
Double (2- the hydroxyethyls)-N- of N, N- (3 '-dodecyloxy -2 '-hydroxypropyl) methylsulfuric acid ammonium methyl, English
Name：N,N-bis(2-hydroxyethyl)-N-(3’-dodecyloxy-2’-hydroxypropyl)methyl ammonium
Methosulfate, another name：Antistatic additive 609.
3,5- di-t-butyl -4- hydroxycinnamic acids, No. CAS：22014-01-3.
Stearamidopropyl dimethyl-beta-hydroxyethyl quaternary ammonium nitrate, English name：Stearamido
Propyldimethyl- β-hydroxyethyl ammonium nitrate, trade name：Cyastat SN, another name：It is antistatic
Agent SN.
The double dodecane esters of thio-2 acid, also known as anti-oxidant DLTP, English name：Thiodipropionicacid
Dilauryl ester, No. CAS：123-28-4.
Three (2,4- di-tert-butyl-phenyl) phosphite ester, English name：Tris(2,4-di-t-butylphenyl)
Phosphite, Chinese nickname：Irgasfos 168, No. CAS：31570-04-4.
Dibutyl hydroxy toluene, English name：Butylated hydroxytoluene, are abbreviated as BHT, and Chinese nickname is
DBPC 2,6 ditertiary butyl p cresol；BHT, No. CAS：128-37-0.
The double hydrazines of thio two propiono of N, N- diacetyl, the double hydrazines of the thio two propionos diacetyl of Chinese nickname are copper suppression
Preparation, it is non-volatile, it is pollution-free.
Inventor is found surprisingly that do compatilizer using monomer graft modification polypropylene, polyacrylic impact resistance is obtained
Improvement has been arrived, meanwhile, itself and damage resistant agent collective effect enhance scratch resistant performance.
Especially the compatilizer is 2- acrylamidos -3 Methylbutanoic acid graft modification polypropylene, methacrylic acid contracting
Water glyceride graft modification polypropylene and 3- isopropenyls-alpha, alpha-dimethyl phenyl isocyanate graft modification polypropylene are according to matter
Amount compares 1:1:It is during 1 blending, better obvious, illustrate between three, there is synergistic function.
In addition, using -4 methoxy benzophenone of ricinoleic acid amide MEA, 2- hydroxyl, 2,2'- dihydroxy -4,4'- diformazans
Epoxide benzophenone -5, the damage resistant agent of 5'- sodium disulfonates three compounding, scratch resistant performance are more excellent, illustrate which has association
With the effect of synergy.Its mechanism need the further research and inquirement of inventor.
According to the preparation method of the present invention, the plastic material for obtaining so that automotive upholstery is provided with following excellent property
Energy：
(1) excellent antistatic property.The present invention is greatly reduced inside gadget by the antistatic additive of addition special formulation
Resistivity, plays excellent antistatic property.
(2) excellent illumination aging resisting performance.Age resister of the present invention by addition special formulation, plastics light shine are old
The property changed is more excellent, not fugitive color.
(3) excellent scratch resistant performance.Damage resistant agent of the present invention by addition special formulation, damage resistant, anti-scratch flower.
(4) safety and environmental protection, low smell.Flavouring of the present invention by addition special formulation, reduces the VOC values of inside gadget,
Smell is low.
Specific embodiment
With reference to embodiment, the invention will be further described.In embodiment, monomer graft modification polypropylene is according to as follows
It is prepared by method：100 kilograms of part polypropylene, 10 kilograms of monomers, 0.1 kilogram of DCP are well mixed；2min is heated at 220 DEG C, is used
Granulator granulation.Respectively using 2- acrylamidos -3 Methylbutanoic acid, GMA and 3- isopropenyls -
α, three kinds of monomers of alpha-alpha-dimethyl phenyl isocyanate, prepare 2- acrylamidos -3 Methylbutanoic acid graft modification polypropylene,
Glycidyl methacrylate graft modified polypropene and 3- isopropenyls-alpha, alpha-dimethyl phenyl isocyanate graft modification
Polypropylene.Jing is determined, and percent grafting is respectively 2.6%, 2.8% and 2.1%.Selected acrylic resin is Sinopec Yizheng Fiber Optical plant
The polypropylene GX-121 of limited company's production.
Embodiment 1
Weigh after each raw material according to correspondence 1 data of embodiment in table 1, stir in adding super mixer, control rotating speed exists
600r/min, 90 DEG C of whipping temp, mixing time 10 minutes, then Jing screw extruder extruding pelletizations, 220 DEG C of extrusion temperature are cold
But, obtain plastic grain；Above-mentioned plastic grain is added into injection mo(u)lding in injection machine, the automotive upholstery is obtained and is changed with environmental protection
Property polypropylene material.
Table 1：Automotive upholstery environment protection modification polypropylene material formula table unit：Kilogram
Embodiment 2
Each raw material is weighed according to correspondence 2 data of embodiment in table 1.The automobile is prepared using the method described in embodiment 1
Inside gadget environment protection modification polypropylene material.
Embodiment 3
Each raw material is weighed according to correspondence 3 data of embodiment in table 1.The automobile is prepared using the method described in embodiment 1
Inside gadget environment protection modification polypropylene material.
Embodiment 4
Each raw material is weighed according to correspondence 4 data of embodiment in table 1.The automobile is prepared using the method described in embodiment 1
Inside gadget environment protection modification polypropylene material.
Embodiment 5
Each raw material is weighed according to correspondence 5 data of embodiment in table 1.The automobile is prepared using the method described in embodiment 1
Inside gadget environment protection modification polypropylene material.
Embodiment 6
Each raw material is weighed according to correspondence 6 data of embodiment in table 1.The automobile is prepared using the method described in embodiment 1
Inside gadget environment protection modification polypropylene material.
Embodiment 7
Each raw material is weighed according to correspondence 7 data of embodiment in table 1.The automobile is prepared using the method described in embodiment 1
Inside gadget environment protection modification polypropylene material.
Test case
The automotive upholstery of embodiment 1～7 is carried out with environment protection modification polypropylene material traditional performance and with scratch resistance
Test, test result are shown in Table 2.
The method of testing of scratch resistant performance is to evaluate scuffing degree using scuffing tester.With a mechanically operated scraper
Show to scrape a line segment figure in ABS plastic.Each scraper is only scraped once in one direction.Then utilize a colorimeter
Measure the misalignment △ E that non-scratch surface is compared.
Test condition is：
Temperature：23 ± 5 DEG C,
Support force：10N,
Scratch speed：1000mm/min,
Scraper diameter：1mm.
Table 2：Automotive upholstery environment protection modification polypropylene material traditional performance and scratch resistant performance test table
| Draw high intensity/Mpa | Bending modulus/Mpa | 23 DEG C of notch impact strength/KJ/m2 | Aberration △ E after scuffing | |
| Method of testing | GB/T1040.1-2006 | GB/T9341-2008 | GB/T1043.1-2008 | |
| Embodiment 1 | 27 | 2690 | 35.1 | 0.22 |
| Embodiment 2 | 27 | 2685 | 32.9 | 0.26 |
| Embodiment 3 | 22 | 2599 | 32.0 | 0.29 |
| Embodiment 4 | 33 | 2790 | 38.8 | 0.17 |
| Embodiment 5 | 31 | 2738 | 38.5 | 0.33 |
| Embodiment 6 | 30 | 2795 | 37.0 | 0.30 |
| Embodiment 7 | 32 | 2752 | 37.3 | 0.41 |
Significantly can be drawn by 2 test data of table, the present invention has preferable resistance to impact and scratch resistant performance, especially
Be embodiment 4 compared with embodiment 5-7, embodiment 4 has used -4 methoxyl group hexichol first of ricinoleic acid amide MEA, 2- hydroxyl
The damage resistant agent effect that ketone, 2,2' dihydroxy 4,4' dimethoxy benzophenone -5,5'- sodium disulfonates are compounded is fairly obvious.
Embodiment 1-3 compared with Example 4 compared with, embodiment 4 used 2- acrylamidos -3 Methylbutanoic acid graft modification polypropylene,
Glycidyl methacrylate graft modified polypropene and 3- isopropenyls-alpha, alpha-dimethyl phenyl isocyanate graft modification
The compatilizer of polypropylene three compounding, tensile strength, bending modulus, notch impact strength are all high than embodiment 1-3 and scratch-resistant
Hinder performance to be also improved.
The above, the only specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, any
Those of ordinary skill in the art disclosed herein technical scope in, the change that can expect without creative work or
Replace, should all be included within the scope of the present invention.Therefore, protection scope of the present invention should be limited with claims
Fixed protection domain is defined.
Claims (7)
1. preparation method of a kind of automotive upholstery with environment protection modification polypropylene material, it is characterised in that comprise the steps：
(1) monomer graft modification polypropylene is prepared, as compatilizer；
(2) by 100 parts of acrylic resin, compatilizer 4-10 parts, damage resistant agent 0.1-0.5 parts, antistatic additive 0.1-0.5 parts resist
Aging dose of 0.1-0.5 part, flavouring 0.1-0.5 parts are well mixed, and stir in adding super mixer, and control rotating speed is in 600-
1000r/min, 90-120 DEG C of whipping temp, mixing time 10-20 minute；
(3) Jing screw extruders extruding pelletization, 200-220 DEG C of extrusion temperature, cooling again, obtains plastic grain；
(4) plastic grain is added into injection mo(u)lding in injection machine, automotive upholstery environment protection modification polypropylene material is obtained；
The damage resistant agent, is made up of by weight following components：Ricinoleic acid amide MEA10-30 parts, -4 methoxyl group of 2- hydroxyls
Benzophenone 5-10 parts, 2,2' dihydroxy 4,4' dimethoxy benzophenone -5,5'- sodium disulfonate 20-40 parts.
2. preparation method as claimed in claim 1, it is characterised in that the monomer graft modification polypropylene is made as follows
It is standby：
(1) 100 parts by weight of polypropylene, 1-15 weight parts monomers, 0.05-0.5 weight portion initiators are well mixed；
(2) 1-5min is heated at 170-220 DEG C, use granulator granulation.
3. preparation method as claimed in claim 1, it is characterised in that：The polyacrylic percent grafting of the monomer graft modification is
0.5-10%.
4. preparation method as claimed in claim 1, it is characterised in that：The compatilizer is 2- acrylamido -3- methyl fourths
Sour graft modification polypropylene, glycidyl methacrylate graft modified polypropene and 3- isopropenyls-alpha, alpha-dimethyl benzene
Based isocyanate graft modification polypropylene is according to mass ratio 1:1:1 blending is formed.
5. preparation method as claimed in claim 1, it is characterised in that：The antistatic additive is selected from palmitamide oxypropyl trimethyl
Ammonium chloride, N, double (2- the hydroxyethyls)-N- of N- (3 '-dodecyloxy -2 '-hydroxypropyl) methylsulfuric acid ammonium methyl or stearoyl
Amine propyl-dimethyl-beta-hydroxyethyl quaternary ammonium nitrate.
6. preparation method as claimed in claim 1, it is characterised in that：The age resister is selected from the double dodecanes of thio-2 acid
The double hydrazines of thio two propiono of ester, three (2,4- di-tert-butyl-phenyls) phosphite ester, dibutyl hydroxy toluene or N, N- diacetyl.
7. preparation method as claimed in claim 1, it is characterised in that：The flavouring is 3,5- di-t-butyl -4- hydroxyl meat
Cinnamic acid.
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| CN103571058A (en) * | 2013-11-22 | 2014-02-12 | 苏州润佳工程塑料股份有限公司 | Reinforced scratching-resistant polypropylene material |
| CN104356509A (en) * | 2014-11-10 | 2015-02-18 | 杭州金州高分子科技有限公司 | High-hardness scratch-resistant high-gloss modified polypropylene (PP) material |
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