CN108752703A - A kind of compound resin and preparation method thereof for arrangements for automotive doors interior trim - Google Patents
A kind of compound resin and preparation method thereof for arrangements for automotive doors interior trim Download PDFInfo
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- CN108752703A CN108752703A CN201810621709.1A CN201810621709A CN108752703A CN 108752703 A CN108752703 A CN 108752703A CN 201810621709 A CN201810621709 A CN 201810621709A CN 108752703 A CN108752703 A CN 108752703A
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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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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Abstract
The present invention relates to auto-parts technical fields, and in particular to is used for the compound resin and preparation method thereof of arrangements for automotive doors interior trim, the preparation method of the compound resin for arrangements for automotive doors interior trim includes the following steps：Organic titanate, organosilicon acid esters are reacted with cetyl trimethylammonium bromide, obtain silicon-titanium photocatalyst；Silicon-titanium photocatalyst and graphene oxide are modified 4- amino -1,2,4- triazoles are compound, obtain compound disinfectant；After acrylic resin, polyvinyl resin, acrylonitrile-butadiene-styrene copolymer, auxiliary agent and compound disinfectant are put into double screw extruder, melting extrusion after injection molding, obtains the compound resin for arrangements for automotive doors interior trim.Interior pernicious gas can be enriched with provided by the present invention for the compound resin of arrangements for automotive doors interior trim, and carry out efficient degradation, achieved the purpose that purify in-vehicle air, improves air quality.
Description
Technical field
The present invention relates to auto-parts technical fields, and in particular to a kind of compound resin for arrangements for automotive doors interior trim and
Preparation method.
Background technology
With the development of the social economy, automobile has become common walking-replacing tool, vehicle when driving, people are in order to improve
Riding comfort often closes vehicle window, and to make car room become closed environment, interior flue gas, human body sweat gas, dust is all
In the surface aggregation of automotive trim panel, peculiar smell is easy tod produce, to make bacterium, germ (acarid, staphylococcus, Legionella, flu
Virus) it largely grows, these harmful substances, as air car recycles, human body is entered by breathing, causes respiratory system sense
The symptoms such as dye, passive protective physical fitness decline, and serious full appearance is dizzy, weak, nauseous especially endanger old man and child special
Greatly.
Currently, people are using periodically wiping automotive interior, to have the function that dedusting, but only it is difficult removal by wiping
Interior bacterium after a period of time after wiping, can grow bacterium, and bacterium is in explosive growth, cannot effectively be solved again
The certainly invasion of bacterium.
Invention content
An object of the present invention is to provide a kind of compound resin for arrangements for automotive doors interior trim, it have long-acting bacteriostatic and
The effect of antibacterial, and it is safe to the human body have no toxic side effect, it is environmental-friendly.It is a kind of for automobile the second object of the present invention is to provide
The preparation method of the compound resin of vehicle door interior trim.
To achieve the goals above, the present invention provides a kind of preparation method of the compound resin for arrangements for automotive doors interior trim,
Include the following steps：
(1) organosilicon acid esters, organic titanate are uniformly mixed, obtain mixed solution A, by cetyl trimethyl bromination
Ammonium is uniformly mixed in water, and mixed solution A then is added dropwise into the mixed system under stirring conditions, after completion of dropwise addition, is added
It is 5.3~6.2 to enter pH adjusting agent regulation system pH, and then mixed system at 100~160 DEG C is sealed to 1~4h of reaction, will produced
Object centrifuge washing is dried, and 1~2h is calcined at 300~550 DEG C, obtains silicon-titanium photocatalyst；
(2) under the conditions of water bath sonicator, amino-polyethyleneglycols are added in the aqueous solution of graphene oxide, add 1-
(3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and N- hydroxysuccinimides, are stirred to react 30~120min, obtain
Graphene oxide is modified to amino-polyethyleneglycols, 4- amino -1,2,4- triazoles and maleic anhydride is then added, at 50~60 DEG C
30~120min of lower water-bath obtains graphene oxide and is modified 4- amino -1,2,4- triazoles；
(3) silicon-titanium photocatalyst is uniformly mixed in water with silane coupling agent, then at 60~80 DEG C reaction 30~
60min is subsequently added into graphene oxide and is modified 4- amino -1,2, and 4- triazoles react 15~30min, obtain under agitation
To compound disinfectant；
(4) by acrylic resin, polyvinyl resin, acrylonitrile-butadiene-styrene copolymer, auxiliary agent and above-mentioned compound
After fungicide puts into double screw extruder, melting extrusion obtains the compound resin for arrangements for automotive doors interior trim.
A kind of compound resin for arrangements for automotive doors interior trim is prepared according to the above method.
Through the above technical solutions, the beneficial effects of the invention are as follows：
By reacting organic titanate, organosilicon acid esters with cetyl trimethylammonium bromide in the present invention, tool is generated
There is porous silicon-titanium photocatalyst of disinfecting mite-removing performance, it has larger specific surface area and more active reaction sites, has
Excellent bactericidal effect.By the way that by graphene and 4- amino -1,2, the progress of 4- triazoles is compound, makes 4- amino -1,2, tri- nitrogen of 4-
Azoles is supported on graphene, can either improve 4- amino -1,2, and the bioactivity of 4- triazoles improves its antibacterial efficiency, and energy
It enough avoids 4- amino -1,2,4- triazoles from falling off from matrix, extends 4- amino -1,2,4- triazole service lifes to reach
Effect.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of preparation method of the compound resin for arrangements for automotive doors interior trim, includes the following steps：
(1) organosilicon acid esters, organic titanate are uniformly mixed, obtain mixed solution A, by cetyl trimethyl bromination
Ammonium is uniformly mixed in water, and mixed solution A then is added dropwise into the mixed system under stirring conditions, after completion of dropwise addition, is added
It is 5.3~6.2 to enter pH adjusting agent regulation system pH, and then mixed system at 100~160 DEG C is sealed to 1~4h of reaction, will produced
Object centrifuge washing is dried, and 1~2h is calcined at 300~550 DEG C, obtains silicon-titanium photocatalyst；
(2) under the conditions of water bath sonicator, amino-polyethyleneglycols are added in the aqueous solution of graphene oxide, add 1-
(3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and N- hydroxysuccinimides, are stirred to react 30~120min, obtain
Graphene oxide is modified to amino-polyethyleneglycols, 4- amino -1,2,4- triazoles and maleic anhydride is then added, at 50~60 DEG C
30~120min of lower water-bath obtains graphene oxide and is modified 4- amino -1,2,4- triazoles；
(3) silicon-titanium photocatalyst is uniformly mixed in water with silane coupling agent, then at 60~80 DEG C reaction 30~
60min is subsequently added into graphene oxide and is modified 4- amino -1,2, and 4- triazoles react 15~30min, obtain under agitation
To compound disinfectant；
(4) by acrylic resin, polyvinyl resin, acrylonitrile-butadiene-styrene copolymer, auxiliary agent and above-mentioned compound
After fungicide puts into double screw extruder, melting extrusion obtains the compound resin for arrangements for automotive doors interior trim.
In step (1), by the way that organosilicon acid esters, organic titanate, cetyl trimethylammonium bromide is anti-in water
It answers, obtains porous silicon-titanium photocatalyst, porous silicon-titanium photocatalyst has larger specific surface area and active reaction sites, and opposite
There is broader light wave reaction interval in photocatalyst of titanium dioxide, improve fungistatic effect of the photocatalyst to indoor bacteria, and energy
The growth for various bacteria of enough disinthibiting has the characteristics that use scope is wide.Under optimum condition, the organic titanate is selected from metatitanic acid
At least one of tetra-ethyl ester, tetramethoxy titanate ester, tetraisopropyl titanate, tetrabutyl titanate, tetra-n-butyl titanate.It is described organic
Esters of silicon acis is selected from least one of quanmethyl silicate, ethyl orthosilicate, tetrabutyl silicate.
The present invention modifies graphene oxide, the water for making graphene oxide have using amidized polyethylene glycol (PEG)
Dissolubility and biocompatibility can be stabilized.By the way that by graphene and 4- amino -1,2, the progress of 4- triazoles is compound,
So that 4- amino -1,2,4- triazoles is supported on graphene, can either improve 4- amino -1,2, the bioactivity of 4- triazoles,
Its antibacterial efficiency is improved, and 4- amino -1,2 can be avoided, 4- triazoles fall off from matrix, extend 4- amino-to reach
The effect of 1,2,4- triazole service lifes.Amidized polyethylene glycol is positively charged, can induce 4- amino -1,2, tri- nitrogen of 4-
Azoles is supported on graphene oxide, not only increases load efficiency, the 4- amino -1,2 of graphene oxide, the biology of 4- triazoles
Activity increases material antibacterial activity, and can form stable composite antibacterial nano material.
By reacting porous silicon-titanium photocatalyst with silane coupling agent, to the carry out surface of porous silicon-titanium photocatalyst
Then modification is modified 4- amino -1,2 in its surface grafting active reactive group with graphene oxide, 4- triazoles carry out anti-
It answers, the active function groups of porous silicon-titanium photocatalyst surface can be combined with the functional group of surface of graphene oxide, be answered
Fungicide is closed, which has superior bactericidal property and safety.Under optimum condition, the silane coupling agent choosing
From Silane coupling agent KH550, silane coupling agent KH560, silane coupling agent KH570, silane coupling agent KH580, silane coupling agent
In KH590, silane coupling agent KH792, silane coupling agent KBM602, silane coupling A 151 and silane coupling A 171 at least
It is a kind of.
In order to further increase the performance, processing performance and service life of the door inner decoration board, preferred stripe
Under part, the present invention also contains auxiliary agent, and the auxiliary agent is selected from antioxidant, lubricant, UV absorbers, finishing agent, resists
At least one of electrostatic agent and colorant.It is further preferred that the ultra-violet absorber is selected from UV-9, UV-531 and UVP-
At least one of 327；The light stabilizer is selected from light stabilizer 292, light stabilizer 622, light stabilizer 770 and light stabilizer
At least one of 944；The one kind of the finishing agent in erucyl amide, glycerin monostearate, oleamide；Institute
It states antistatic agent and is selected from least one of polyether ester amides, epoxypropane copolymerization object and ethylene oxide；The colorant choosing
From at least one of carbon black, lemon yellow, indigo, phthalocyanine green.The antioxidant is selected from Hinered phenols antioxidant, thiosulfates
At least one of kind antioxidant and phosphite ester kind antioxidant, it is further preferred that the Hinered phenols antioxidant is antioxygen
Agent 1010, the thiosulfates kind antioxidant are anti-oxidant DLTP, and the phosphite ester kind antioxidant is irgasfos 168.Institute
It is in polyethylene wax, calcium stearate, zinc stearate, lignite wax, ethylene bis stearamide, pentaerythritol stearate to state lubricant
At least one.
The present invention will be described in detail by way of examples below.In following embodiment, graphene oxide it is a concentration of
10mg/mL。
Embodiment 1
A kind of compound resin for arrangements for automotive doors interior trim is made of the substance of following parts by weight：70 weight of acrylic resin
Measure part, 95 parts by weight of polyvinyl resin, 2.5 parts by weight of tetraethyl titanate, 8 parts by weight of tetrabutyl silicate, cetyl trimethyl
10 parts by weight of ammonium bromide, 5 parts by weight of hydrochloric acid (2M), 2 parts by weight of Silane coupling agent KH550,3 parts by weight of amino-polyethyleneglycols, 1-
10 parts by weight of (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, 12 parts by weight of N- hydroxysuccinimides, oxidation stone
15 parts by weight of black alkene, 5 parts by weight of 4- amino-1,2,4-triazols, 2 parts by weight of acrylonitrile-butadiene-styrene copolymer,
UVP-3271 parts by weight, 1 parts by weight of glycerin monostearate, 1 parts by weight of polyether ester amides, resist 7701 parts by weight of light stabilizer
10101 parts by weight of oxygen agent.
The preparation method of the compound resin for arrangements for automotive doors interior trim, steps are as follows：
(1) tetraethyl titanate, tetrabutyl silicate are uniformly mixed, obtain mixed solution A, by cetyl trimethyl bromination
Ammonium is uniformly mixed in water, and mixed solution A then is added dropwise into the mixed system under stirring conditions, after completion of dropwise addition, is added
It is 6.2 to enter hydrochloric acid regulation system pH, and then mixed system at 150 DEG C is sealed to reaction 3h, product centrifuge washing is dried, and
1.5h is calcined at 400 DEG C, obtains silicon-titanium photocatalyst；
(2) under the conditions of water bath sonicator, amino-polyethyleneglycols are added in the aqueous solution of graphene oxide, add 1-
(3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and N- hydroxysuccinimides, are stirred to react 90min, obtain ammonia
Then 4- amino -1,2,4- triazoles and maleic anhydride is added in the polyethyleneglycol modified graphene oxide of base, water-bath is anti-at 60 DEG C
60min is answered, graphene oxide is obtained and is modified 4- amino -1,2,4- triazoles；
(3) silicon-titanium photocatalyst is uniformly mixed in water with Silane coupling agent KH550, is then reacted at 80 DEG C
30min is subsequently added into graphene oxide and is modified 4- amino -1,2, and 4- triazoles react 30min, answered under agitation
Close fungicide；
(4) acrylic resin, polyvinyl resin, acrylonitrile-butadiene-styrene copolymer, UVP-327, light are stablized
After agent 770, glycerin monostearate, polyether ester amides, antioxidant 1010 and above-mentioned compound disinfectant input double screw extruder,
(technique of melting extrusion is for melting extrusion：Extrusion temperature be 200 DEG C, screw speed 350r/min, vacuum degree be-
0.08MPa), the compound resin for arrangements for automotive doors interior trim is obtained.
Embodiment 2
A kind of compound resin for arrangements for automotive doors interior trim is made of the substance of following parts by weight：75 weight of acrylic resin
Measure part, 90 parts by weight of polyvinyl resin, 3 parts by weight of tetraethyl titanate, 5 parts by weight of tetrabutyl silicate, cetyl trimethyl bromine
Change 8 parts by weight of ammonium, 2 parts by weight of hydrochloric acid (2M), 1.5 parts by weight of Silane coupling agent KH550,5 parts by weight of amino-polyethyleneglycols, 1-
12 parts by weight of (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, 12 parts by weight of N- hydroxysuccinimides, oxidation stone
18 parts by weight of black alkene, 10 parts by weight of 4- amino-1,2,4-triazols, 0.5 parts by weight of acrylonitrile-butadiene-styrene copolymer,
UV-5311 parts by weight, 2 parts by weight of glycerin monostearate, 1 parts by weight of polyether ester amides, resist 7700.5 parts by weight of light stabilizer
10101 parts by weight of oxygen agent.
The preparation method of the compound resin for arrangements for automotive doors interior trim, steps are as follows：
(1) tetraethyl titanate, tetrabutyl silicate are uniformly mixed, obtain mixed solution A, by cetyl trimethyl bromination
Ammonium is uniformly mixed in water, and mixed solution A then is added dropwise into the mixed system under stirring conditions, after completion of dropwise addition, is added
It is 5.5 to enter hydrochloric acid regulation system pH, and then mixed system at 120 DEG C is sealed to reaction 3h, product centrifuge washing is dried, and
1h is calcined at 350 DEG C, obtains silicon-titanium photocatalyst；
(2) under the conditions of water bath sonicator, amino-polyethyleneglycols are added in the aqueous solution of graphene oxide, add 1-
(3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and N- hydroxysuccinimides, are stirred to react 120min, obtain ammonia
Then 4- amino -1,2,4- triazoles and maleic anhydride is added in the polyethyleneglycol modified graphene oxide of base, water-bath is anti-at 50 DEG C
90min is answered, graphene oxide is obtained and is modified 4- amino -1,2,4- triazoles；
(3) silicon-titanium photocatalyst is uniformly mixed in water with Silane coupling agent KH550, is then reacted at 70 DEG C
45min is subsequently added into graphene oxide and is modified 4- amino -1,2, and 4- triazoles react 15~30min, obtain under agitation
To compound disinfectant；
(4) by acrylic resin, polyvinyl resin, acrylonitrile-butadiene-styrene copolymer, UV-531, light stabilizer
770, after glycerin monostearate, polyether ester amides, antioxidant and above-mentioned compound disinfectant input double screw extruder, melting is squeezed
Go out that (technique of melting extrusion is：Extrusion temperature is 200 DEG C, screw speed 350r/min, and vacuum degree is -0.08MPa), it obtains
Compound resin for arrangements for automotive doors interior trim.
Embodiment 3
A kind of compound resin for arrangements for automotive doors interior trim is made of the substance of following parts by weight：65 weight of acrylic resin
Measure part, 100 parts by weight of polyvinyl resin, 2 parts by weight of tetraethyl titanate, 10 parts by weight of tetrabutyl silicate, cetyl trimethyl
12 parts by weight of ammonium bromide, 8 parts by weight of hydrochloric acid (2M), silane coupling agent KH5701.2 parts by weight, 3 parts by weight of amino-polyethyleneglycols,
8 parts by weight of 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, 15 parts by weight of N- hydroxysuccinimides, oxidation
18 parts by weight of graphene, 10 parts by weight of 4- amino-1,2,4-triazols, 3 parts by weight of acrylonitrile-butadiene-styrene copolymer,
7700.5 parts by weight of light stabilizer, 0.5 parts by weight of glycerin monostearate, 1 parts by weight of antioxidant 1010.
The preparation method of the compound resin for arrangements for automotive doors interior trim, steps are as follows：
(1) tetraethyl titanate, tetrabutyl silicate are uniformly mixed, obtain mixed solution A, by cetyl trimethyl bromination
Ammonium is uniformly mixed in water, and mixed solution A then is added dropwise into the mixed system under stirring conditions, after completion of dropwise addition, is added
It is 5.8 to enter hydrochloric acid regulation system pH, and then mixed system at 120 DEG C is sealed to reaction 3h, product centrifuge washing is dried, and
2h is calcined at 450 DEG C, obtains silicon-titanium photocatalyst；
(2) under the conditions of water bath sonicator, amino-polyethyleneglycols are added in the aqueous solution of graphene oxide, add 1-
(3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and N- hydroxysuccinimides, are stirred to react 60min, obtain ammonia
Then 4- amino -1,2,4- triazoles and maleic anhydride is added in the polyethyleneglycol modified graphene oxide of base, water-bath is anti-at 60 DEG C
60min is answered, graphene oxide is obtained and is modified 4- amino -1,2,4- triazoles；
(3) silicon-titanium photocatalyst is uniformly mixed in water with silane coupling agent KH570, is then reacted at 80 DEG C
45min is subsequently added into graphene oxide and is modified 4- amino -1,2, and 4- triazoles react 25min, answered under agitation
Close fungicide；
(4) by acrylic resin, polyvinyl resin, acrylonitrile-butadiene-styrene copolymer, light stabilizer 770, list
After tristerin, antioxidant and above-mentioned compound disinfectant input double screw extruder, the melting extrusion (technique of melting extrusion
For：Extrusion temperature is 200 DEG C, screw speed 350r/min, and vacuum degree is -0.08MPa), it obtains being used for arrangements for automotive doors interior trim
Compound resin.
Embodiment 4
A kind of compound resin for arrangements for automotive doors interior trim is made of the substance of following parts by weight：80 weight of acrylic resin
Measure part, 80 parts by weight of polyvinyl resin, 5 parts by weight of tetramethoxy titanate ester, 3 parts by weight of ethyl orthosilicate, cetyl trimethyl bromine
Change 5 parts by weight of ammonium, 10 parts by weight of hydrochloric acid (2M), silane coupling agent KH5703 parts by weight, 5 parts by weight of amino-polyethyleneglycols, 1- (3-
Dimethylamino-propyl) 15 parts by weight of -3- ethyl-carbodiimide hydrochlorides, 20 parts by weight of N- hydroxysuccinimides, graphite oxide
10 parts by weight of alkene, 3 parts by weight of 4- amino-1,2,4-triazols, 0.5 parts by weight of acrylonitrile-butadiene-styrene copolymer,
UVP-3272 parts by weight, 2 parts by weight of glycerin monostearate, 1 parts by weight of polyether ester amides, resist 7701 parts by weight of light stabilizer
10102 parts by weight of oxygen agent.
The preparation method of the compound resin for arrangements for automotive doors interior trim, steps are as follows：
(1) tetramethoxy titanate ester, ethyl orthosilicate are uniformly mixed, obtain mixed solution A, by cetyl trimethyl bromination
Ammonium is uniformly mixed in water, and mixed solution A then is added dropwise into the mixed system under stirring conditions, after completion of dropwise addition, is added
It is 6.2 to enter hydrochloric acid regulation system pH, and then mixed system at 100 DEG C is sealed to reaction 1h, product centrifuge washing is dried, and
1h is calcined at 550 DEG C, obtains silicon-titanium photocatalyst；
(2) under the conditions of water bath sonicator, amino-polyethyleneglycols are added in the aqueous solution of graphene oxide, add 1-
(3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and N- hydroxysuccinimides, are stirred to react 30min, obtain ammonia
Then 4- amino -1,2,4- triazoles and maleic anhydride is added in the polyethyleneglycol modified graphene oxide of base, water-bath is anti-at 60 DEG C
30min is answered, graphene oxide is obtained and is modified 4- amino -1,2,4- triazoles；
(3) silicon-titanium photocatalyst is uniformly mixed in water with silane coupling agent KH570, is then reacted at 60 DEG C
60min is subsequently added into graphene oxide and is modified 4- amino -1,2, and 4- triazoles react 30min, answered under agitation
Close fungicide；
(4) acrylic resin, polyvinyl resin, acrylonitrile-butadiene-styrene copolymer, UVP-327, light are stablized
After agent 770, glycerin monostearate, polyether ester amides, antioxidant 1010 and above-mentioned compound disinfectant input double screw extruder,
(technique of melting extrusion is for melting extrusion：Extrusion temperature be 200 DEG C, screw speed 350r/min, vacuum degree be-
After 0.08MPa), the compound resin for arrangements for automotive doors interior trim is obtained.
Embodiment 5
A kind of compound resin for arrangements for automotive doors interior trim is made of the substance of following parts by weight：60 weight of acrylic resin
Measure part, 120 parts by weight of polyvinyl resin, 1 parts by weight of tetrabutyl titanate, 12 parts by weight of ethyl orthosilicate, cetyl front three
15 parts by weight of base ammonium bromide, 1 parts by weight of hydrochloric acid (2M), silane coupling agent KH5701 parts by weight, 3 parts by weight of amino-polyethyleneglycols,
5 parts by weight of 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, 10 parts by weight of N- hydroxysuccinimides, oxidation
20 parts by weight of graphene, 12 parts by weight of 4- amino-1,2,4-triazols, 3 parts by weight of acrylonitrile-butadiene-styrene copolymer.
The preparation method of the compound resin for arrangements for automotive doors interior trim, steps are as follows：
(1) tetrabutyl titanate, ethyl orthosilicate are uniformly mixed, obtain mixed solution A, by cetyl trimethyl bromine
Change ammonium to be uniformly mixed in water, mixed solution A then is added dropwise into the mixed system under stirring conditions, after completion of dropwise addition,
It is 5.3 that hydrochloric acid regulation system pH, which is added, and then mixed system at 160 DEG C is sealed to reaction 4h, product centrifuge washing is dried,
And 2h is calcined at 300 DEG C, obtain silicon-titanium photocatalyst；
(2) under the conditions of water bath sonicator, amino-polyethyleneglycols are added in the aqueous solution of graphene oxide, add 1-
(3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and N- hydroxysuccinimides, are stirred to react 60min, obtain ammonia
Then 4- amino -1,2,4- triazoles and maleic anhydride is added in the polyethyleneglycol modified graphene oxide of base, water-bath is anti-at 50 DEG C
120min is answered, graphene oxide is obtained and is modified 4- amino -1,2,4- triazoles；
(3) silicon-titanium photocatalyst is uniformly mixed in water with silane coupling agent KH570, is then reacted at 80 DEG C
30min is subsequently added into graphene oxide and is modified 4- amino -1,2, and 4- triazoles react 15min, answered under agitation
Close fungicide；
(4) by acrylic resin, polyvinyl resin, acrylonitrile-butadiene-styrene copolymer, auxiliary agent and above-mentioned compound
After fungicide puts into double screw extruder, (technique of melting extrusion is for melting extrusion：Extrusion temperature is 200 DEG C, and screw speed is
350r/min, vacuum degree are -0.08MPa), obtain the compound resin for arrangements for automotive doors interior trim.
Comparative example 1
A kind of compound resin for arrangements for automotive doors interior trim is made of the substance of following parts by weight：70 weight of acrylic resin
Measure part, 95 parts by weight of polyvinyl resin, 2.5 parts by weight of tetraethyl titanate, 8 parts by weight of tetrabutyl silicate, cetyl trimethyl
10 parts by weight of ammonium bromide, 5 parts by weight of hydrochloric acid (2M), 2 parts by weight of Silane coupling agent KH550, acrylonitrile-butadiene-styrene (ABS) are total
2 parts by weight of polymers, UVP-3271 parts by weight, 7701 parts by weight of light stabilizer, 1 parts by weight of glycerin monostearate, polyether ester acyl
1 parts by weight of amine, 1 parts by weight of antioxidant 1010.
The preparation method of the compound resin for arrangements for automotive doors interior trim, steps are as follows：
(1) tetraethyl titanate, tetrabutyl silicate are uniformly mixed, obtain mixed solution A, by cetyl trimethyl bromination
Ammonium is uniformly mixed in water, and mixed solution A then is added dropwise into the mixed system under stirring conditions, after completion of dropwise addition, is added
It is 6.2 to enter hydrochloric acid regulation system pH, and then mixed system at 150 DEG C is sealed to reaction 3h, product centrifuge washing is dried, and
1.5h is calcined at 400 DEG C, obtains silicon-titanium photocatalyst；
(2) acrylic resin, polyvinyl resin, acrylonitrile-butadiene-styrene copolymer, UVP-327, light are stablized
Agent 770, glycerin monostearate, polyether ester amides, antioxidant 1010 and above-mentioned silicon-titanium photocatalyst put into double screw extruder
Afterwards, (technique of melting extrusion is for melting extrusion：Extrusion temperature be 200 DEG C, screw speed 350r/min, vacuum degree be-
After 0.08MPa), the compound resin for arrangements for automotive doors interior trim is obtained.
Comparative example 2
A kind of compound resin for arrangements for automotive doors interior trim is made of the substance of following parts by weight：70 weight of acrylic resin
Measure part, 95 parts by weight of polyvinyl resin, 2.5 parts by weight of tetraethyl titanate, 10 parts by weight of cetyl trimethylammonium bromide, hydrochloric acid
(2M) 5 parts by weight, 2 parts by weight of Silane coupling agent KH550,5 parts by weight of 4- amino-1,2,4-triazols, acrylonitrile-butadiene-
2 parts by weight of styrol copolymer, UVP-3271 parts by weight, 7701 parts by weight of light stabilizer, 1 parts by weight of glycerin monostearate,
1 parts by weight of polyether ester amides, 1 parts by weight of antioxidant 1010.
The preparation method of the compound resin for arrangements for automotive doors interior trim, steps are as follows：
(1) cetyl trimethylammonium bromide is uniformly mixed in water, then under stirring conditions to the mixture
Tetraethyl titanate is added dropwise in system, after completion of dropwise addition, it is 6.2 that hydrochloric acid regulation system pH, which is added, then by mixed system at 150 DEG C
Sealing reaction 3h, product centrifuge washing is dried, and calcine 1.5h at 400 DEG C, obtains photocatalyst；
(3) photocatalyst is uniformly mixed in water with Silane coupling agent KH550,30min is then reacted at 80 DEG C, then
4- amino -1,2 is added, 4- triazoles react 30min, obtain compound disinfectant under agitation；
(4) acrylic resin, polyvinyl resin, acrylonitrile-butadiene-styrene copolymer, UVP-327, light are stablized
After agent 770, glycerin monostearate, polyether ester amides, antioxidant 1010 and above-mentioned compound disinfectant input double screw extruder,
(technique of melting extrusion is for melting extrusion：Extrusion temperature be 200 DEG C, screw speed 350r/min, vacuum degree be-
0.08MPa), the compound resin for arrangements for automotive doors interior trim is obtained.
After compound resin (3cm × 3cm × 2mm) in Examples 1 to 5 and comparative example 1~2 is cleaned with acetone, ethyl alcohol, use
75% ethyl alcohol impregnates 2h to kill the bacterium of sample surfaces, is placed in culture dish the natural air drying in super-clean bench.Then each
200 μ L bacterium solutions (10 are added dropwise in sample surfaces5CFU/mL), cultivated for 24 hours in 37 DEG C of incubators after being covered with the sealed membrane of sterilizing.With
The physiological saline containing 0.3% Tween-80 of 20mL sterilizings thoroughly cleans surface and obtains bacterium solution, and by bacterium solution dilute 10 times and
100 times, 100 times of undiluted, 10 times of dilution, dilution bacterium solution 0.2mL is taken to be coated uniformly on solid medium respectively, 37 DEG C of cultures
2h, 12h and 7d are cultivated respectively, calculates the antibiotic rate of sample, and experimental result is as shown in table 1.
The calculation formula of antibiotic rate is：
Antibiotic rate=(nControl-nExperiment)/nControl× 100%
Wherein, nControlFor blank control group clump count, nExperimentFor experimental group clump count；
Experimental group is the compound resin (3cm × 3cm × 2mm) in Examples 1 to 5 and comparative example 1~2 in this experiment, right
According to a group slide, experimental result is as shown in table 1.
Table 1：
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (6)
1. a kind of preparation method of compound resin for arrangements for automotive doors interior trim, which is characterized in that include the following steps：
(1) organosilicon acid esters, organic titanate are uniformly mixed, obtain mixed solution A, cetyl trimethylammonium bromide is existed
It is uniformly mixed in water, mixed solution A then is added dropwise into the mixed system under stirring conditions, after completion of dropwise addition, pH is added
Conditioning agent regulation system pH is 5.3~6.2, then seal at 100~160 DEG C mixed system and reacts 1~4h, by product from
The heart washs drying, and 1~2h is calcined at 300~550 DEG C, obtains silicon-titanium photocatalyst；
(2) under the conditions of water bath sonicator, amino-polyethyleneglycols are added in the aqueous solution of graphene oxide, add 1- (3- bis-
Methylaminopropyl) -3- ethyl-carbodiimide hydrochlorides and N- hydroxysuccinimides, it is stirred to react 30~120min, obtains ammonia
Then 4- amino -1,2,4- triazoles and maleic anhydride, the water at 50~60 DEG C is added in the polyethyleneglycol modified graphene oxide of base
Bath 30~120min of reaction, obtains graphene oxide and is modified 4- amino -1,2,4- triazoles；
(3) silicon-titanium photocatalyst is uniformly mixed in water with silane coupling agent, 30~60min is then reacted at 60~80 DEG C,
It is subsequently added into graphene oxide and is modified 4- amino -1,2,4- triazoles react 15~30min, obtain compound under agitation
Fungicide；
(4) by acrylic resin, polyvinyl resin, acrylonitrile-butadiene-styrene copolymer, auxiliary agent and above-mentioned composite bactericidal
After agent puts into double screw extruder, melting extrusion obtains the compound resin for arrangements for automotive doors interior trim.
2. the preparation method of the compound resin according to claim 1 for arrangements for automotive doors interior trim, which is characterized in that described
Organic titanate is in tetraethyl titanate, tetramethoxy titanate ester, tetraisopropyl titanate, tetrabutyl titanate, tetra-n-butyl titanate
At least one.
3. the preparation method of the compound resin according to claim 1 for arrangements for automotive doors interior trim, which is characterized in that described
Organosilicon acid esters is selected from least one of quanmethyl silicate, ethyl orthosilicate, tetrabutyl silicate.
4. the preparation method of the compound resin according to claim 1 for arrangements for automotive doors interior trim, which is characterized in that described
Silane coupling agent is selected from Silane coupling agent KH550, silane coupling agent KH560, silane coupling agent KH570, silane coupling agent
KH580, silane coupling agent KH590, silane coupling agent KH792, silane coupling agent KBM602, silane coupling A 151 and silane are even
Join at least one of agent A171.
5. the preparation method of the compound resin according to claim 1 for arrangements for automotive doors interior trim, which is characterized in that described
Auxiliary agent is selected from least one of antioxidant, lubricant, UV absorbers, finishing agent, antistatic agent and colorant.
6. a kind of compound resin for arrangements for automotive doors interior trim, which is characterized in that according to any one of Claims 1 to 5 institute
The preparation method stated is prepared.
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| CN201810621709.1A CN108752703A (en) | 2018-06-15 | 2018-06-15 | A kind of compound resin and preparation method thereof for arrangements for automotive doors interior trim |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810621709.1A CN108752703A (en) | 2018-06-15 | 2018-06-15 | A kind of compound resin and preparation method thereof for arrangements for automotive doors interior trim |
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| Country | Link |
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2018
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