CN105694371A - Resin composition and preparation method and application thereof - Google Patents
Resin composition and preparation method and application thereof Download PDFInfo
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- CN105694371A CN105694371A CN201610222001.XA CN201610222001A CN105694371A CN 105694371 A CN105694371 A CN 105694371A CN 201610222001 A CN201610222001 A CN 201610222001A CN 105694371 A CN105694371 A CN 105694371A
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to a novel resin composition and a preparation method and application thereof. The novel resin composition comprises resin masterbatch, modified calcium sulfate whiskers, a stabilizer, a toughener, nano carbon black, an organic silane coupling agent, dilauryl thiodipropionate, a bi-component antioxidant, an adhesion promoter, a solidifying agent and an aid. The resin composition is imparted excellent mechanical properties, weatherability and the like through synergy and mutual promotion of unique component selection, preparation method and the like; the resin composition is applicable to various specific fields and has great application potential and industrial production prospect.
Description
Technical field
The present invention relates to a kind of resin combination, relate more particularly to a kind of resin combination with high intensity and excellent weather resistance and its production and use, belong to resin combination technical field。
Background technology
The harshness of the development along with science and technology and raising and the applied environment day by day to materials application requirement, thus there being increasingly higher performance requirement to resin combination。Therefore, development of new, the resin combination with superperformance there is urgent demand。
In many performances of resin combination, intensity and weatherability are very important two indices, and a lot of fields are desirable that material has high intensity and excellent weatherability, for instance as construction material, it is necessary to excellent weatherability, thus the longer time can be used。And for some engineering material field, then need resin combination to have good intensity, with satisfied application requirement。
Typically, it is applied to our daily life generally occur with the form of resin with the resin combination in work, for instance engineering resin, electrician's resin, insulating resin etc.。
In order to meet the requirement of high intensity and excellent weather resistance, resin combination has been carried out substantial amounts of further investigation by people, and achieves many achievements, for instance:
CN1040806A discloses a kind of weather resisteant polyacetal resin composite, including: (A) polyacetal resin, (B) accounting for weathering (light) stabilizer of total composition 0.01-0.5% weight, (C) accounts for the acrylate of total composition 1-40% weight。
WO2006084611A discloses a kind of weatherability with excellence, high sun heat radiation permeability, to the moulded goods being made up of multilamellar from ground-launched thermal-radiating effective stop and high mechanical properties, wherein each layer is made up of following material: layer 1 is the copolymer of olefin polymer or ethyl vinyl acetate polymer or alkene and ethyl vinyl acetate, layer 2 is the fabric of the fiber of the drawn being made up of thermoplastic polymer, layer 3 is the copolymer of olefin polymer or ethyl vinyl acetate polymer or alkene and ethyl vinyl acetate, layer 4 is adhesion promotor, layer 5 is polymethyl methacrylate。
CN101143945A discloses the silane crosslinked polyethylene plastic of a kind of color weatherable, its component and parts by weight include: polyvinyl resin 100 parts, weather-proof auxiliary agent 0.01-3 part, metal-oxide 0.1-20 part, color masterbatch 0.01-10 part, silane crosslinker 0.5-3 part, initiator 0.01-1.5 part, antioxidant 0.02-2 part, matal deactivator 0.05-1 part, catalyst 0.01-5 part。It can produce the organosilane crosslinked polyethylene insulation plastics meeting the weather-proof requirement of aerial cable of shades of colour, particularly Lycoperdon polymorphum Vitt product can be that cable environment of accepting heat radiation degree is relatively low, aerial cable current-carrying capacity can be improved, meet the needs of aerial cable different levels。
CN104829964A discloses the modified plastics that a kind of hot strength high-weatherability is good, and it is made up of the raw material of following weight portion: polrvinyl chloride 65-70, nylon 1215-20, Merlon 20-25, nano antimony tin oxide 4-8, nanometer titanium dioxide 1-2, waste oil 2-3, ten dihydroxystearic acid 0.3-0.7, alumina-silicate ceramic fibre 1-3, plasticized starch 2-4, tungsten disulfide 0.1-0.3, maleic anhydride grafted polyethylene 0.5-1.5, dehydrated alcohol are appropriate；The advantages such as its plastics good toughness prepared, bending strength are high, tensile property is high, big, low, the easy-formation of good weatherability, cost of tearing strength。
CN104497527A discloses a kind of high-weatherability PC/ABS engineering plastics, is made up of by weight percentage following component: aromatic polycarbonate: 60-80%；Acrylonitrile, butadiene, styrene copolymer: 10-40%；Compatilizer: 1-3%；Antioxidant: 0.5-1.2%；The steady agent of light: .5-1.2%；Impact modifier: 1-3%；Lubricant: 0-1%, described compatilizer is polysiloxanes-esters of acrylic acid compatilizer, and antioxidant is phosphorous acid lipid antioxidant, the steady agent of light is the steady agent of hindered amines light, lubricant is TAF, and impact modifier is methyl methacrylate, butadiene and cinnamic terpolymer modifying agent。Described PC/ABS engineering plastics good weatherability, with should be extensive, be particularly suited for electronic product casing。
The preparation method that CN103467704A discloses a kind of high-weathering-resistance polyurethane rigid foam; the monohydroxy poly(ethylene oxide) and 1 that a, addition are measured; 4-butanediol; the dibutyl tin laurate of catalytic amount; tripolycyanamide, is full of nitrogen in still or noble gas is protected, heat 40-60 DEG C; it is sufficiently stirred for 3-6 hour, is cooled to 25 DEG C；B, adding poly-4 in the product obtained, 4 '-'-diphenylmethane diisocyanate, poly-isophorone diisocyanate, organic silicone oil, triethylamine, suitable quantity of water, high-speed stirred is to foaming；C, at 40-60 DEG C ripening 501-80 minute, the demoulding, obtains high-weathering-resistance polyurethane rigid foam plastic goods, and described method is by blended by IPDI and MDI, adjust each related raw material formula, technological operation, product color inhibition, fast light, weather resistance good, have and suitable draw high intensity and ductility, technological operation is simple, and cost is controlled, is suitable for industrialized production。
As mentioned above, prior art discloses the multiple resin combination with some strength and/or weatherability, but for novel resin combination heat, still suffer from continuing necessity of research, this not only has urgent researching value, also having good economic benefit and commercial Application potentiality, this power place that present invention is accomplished just and basis are leaned on。
Summary of the invention
In order to seek the resin combination with good strength and excellent weather resistance, this is conducted in-depth research by the present inventor, after having paid a large amount of creative work, thus completing the present invention。
Specifically, first aspect, the present invention relates to a kind of novel resin composition, described novel resin composition includes resin concentrates, wastewaters with modified calcium sulfate whiskers, stabilizer, toughener, nano carbon black, organo silane coupling agent, thiodipropionic acid dilauryl cinnamic acid ester, bi-component antioxidant, adhesive accelerant, firming agent and auxiliary agent。
Wherein, with parts by weight, described novel resin composition includes following component:
In described novel resin composition, the weight portion of described resin concentrates is 80-90 part, for instance can be 80 parts, 85 parts or 90 parts。
Described resin concentrates is the mixture of bisphenol A type epoxy resin, methacrylic acid-butadiene-styrene terpolymer (MBS resin) and polrvinyl chloride。Wherein, the weight ratio of bisphenol A type epoxy resin, methacrylic acid-butadiene-styrene terpolymer (MBS resin) and polrvinyl chloride is 2:1:1。
Wherein, bisphenol A type epoxy resin, methacrylic acid-butadiene-styrene terpolymer (MBS resin) and polrvinyl chloride are all the conventional substances in field of polymer technology, can be buied by multiple commercial channel, no longer be described in detail at this。
In described novel resin composition, the weight portion of wastewaters with modified calcium sulfate whiskers is 0.5-1 part, for instance can be 0.5 part, 0.7 part, 0.9 part or 1 part。
Described wastewaters with modified calcium sulfate whiskers is to prepare according to the preparation method comprised the steps:
A1: calcium sulfate crystal whiskers is cut into the length of 0.2-0.5mm, joins in dehydrated alcohol, ultrasonic waves for cleaning 20-30 minute, filters, and after cleaning, calcium sulfate crystal whiskers deionized water wash 2-3 time, pulls out, fully dry, obtains clean calcium sulfate crystal whiskers；
A2: cleaning calcium sulfate crystal whiskers is joined in dehydrated alcohol, it is slow added into the ethanol solution of positive isopropyl silicate, stirring reaction 40-60 minute, filter, gained whisker deionized water is fully washed 3-4 time, dry, the dried whisker obtained is calcined 30-40 minute at 300-340 DEG C, naturally cool to room temperature, namely obtain described wastewaters with modified calcium sulfate whiskers。
Wherein, in described step A1, the consumption of dehydrated alcohol is not particularly limited, as long as it can fully clean calcium sulfate crystal whiskers。
Wherein, in described step A2, clean calcium sulfate crystal whiskers is joined as, in its dehydrated alcohol of quality 8-10 times, then adding the ethanol solution of positive isopropyl silicate。
Wherein, in described step A2, the mass ratio of described clean calcium sulfate crystal whiskers and positive isopropyl silicate is 1:0.4-0.6, for instance can be 1:0.4,1:0.5 or 1:0.6。
Wherein, in described step A2, in the ethanol solution of described positive isopropyl silicate, the mass percent concentration of positive isopropyl silicate is 20-30%。
In described novel resin composition, the weight portion of stabilizer is 1-2 part, for instance can be 1 part, 1.5 parts or 2 parts。
Wherein, any in di-n-butyltin dilaurate, dimercapto 2-ethyl hexyl ethanoate stannous methide or trisnonyl phenyl phosphite of described stabilizer, it is most preferred that for dimercapto 2-ethyl hexyl ethanoate stannous methide。
In described novel resin composition, the weight portion of toughener is 2-3 part, for instance can be 2 parts, 2.5 parts or 3 parts。
Described toughener is any one in latex powder, poly-epsilon-caprolactone or MBS terpolymer (MBS), it is most preferred that for MBS。Described MBS is the conventional substances in this area, can be obtained by multiple commercial channel, no longer be described in detail at this。
In described novel resin composition, the weight portion of nano carbon black is 0.4-0.8 part, for instance can be 0.4 part, 0.6 part or 0.8 part。
Wherein, described nano carbon black is the conventional substances in field of inorganic materials, can be obtained by multiple commercial channel, no longer be described in detail at this。
In described novel resin composition, the weight portion of organo silane coupling agent is 1.4-2 part, for instance can be 1.4 parts, 1.6 parts, 1.8 parts or 2 parts。
Wherein, described organo silane coupling agent is methacryloxypropyl trimethoxy silane, phenylaminomethyl triethoxysilane, β-(3,4-epoxycyclohexyl) any one in ethyl trimethoxy silane or γ-glycidyl ether oxygen propyl trimethoxy silicane, it most preferably is β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane。
In described novel resin composition, the weight portion of thiodipropionic acid dilauryl cinnamic acid ester is 2-3 part, for instance can be 2 parts, 2.5 parts or 3 parts。
In described novel resin composition, the weight portion of bi-component antioxidant is 1-1.6 part, for instance can be 1 part, 1.3 parts or 1.6 parts。
Wherein, described bi-component antioxidant is three (2,4-di-tert-butyl-phenyl) phosphite ester and 1,3,5-trimethyl-2 of mass ratio 1:1-2, the mixture of 4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene。
In described novel resin composition, the weight portion of adhesive accelerant is 0.5-0.8 part, for instance can be 0.5 part, 0.6 part, 0.7 part or 0.8 part。
Wherein, described adhesive accelerant is following formula (I) compound or (II) compound,
It most preferably is described formula (I) compound。
In described novel resin composition, the weight portion of firming agent is 0.6-1 part, for instance can be 0.6 part, 0.8 part or 1 part。
Wherein, described firming agent is 3,3'-dimethyl-4,4'-diamino-dicyclohexyl methane, 5-amino-1, any one in 3,3-3-methyl cyclohexanol methylamines or 4,4'-diamino bicyclic hexyl methane, it most preferably is 3,3'-dimethyl-4,4'-diamino-dicyclohexyl methane。
In described novel resin composition, the weight portion of auxiliary agent is 0.8-1.2 part, for instance can be 0.8 part, 1 part or 1.2 parts。
Wherein, described auxiliary agent is the mass mixing thing such as grade of carboxyethyl cellulose and hydroxyapatite, and the granularity of described hydroxyapatite is 100-150 order。
Second aspect, the preparation method that the invention still further relates to described novel resin composition, described preparation method comprises the steps:
S1: according to the weight ratio of 2:1:1, weigh phenol A type epoxy resin, methacrylic acid-butadiene-styrene terpolymer (MBS resin) and polrvinyl chloride, and use high-speed mixer to carry out full and uniform mixing, obtain 80-90 parts by weight resin masterbatch；
S2: add the part by weight modified calcium sulfate crystal whiskers of 0.5-1,1-2 weight portion stabilizer, 2-3 weight portion toughener, 0.4-0.8 weight portion nano carbon black, 2-3 weight portion thiodipropionic acid dilauryl cinnamic acid ester, 1-1.6 weight portion bi-component antioxidant, 0.5-0.8 weight portion adhesive accelerant, 6-8 weight portion auxiliary agent in above-mentioned resin concentrates and be the organo silane coupling agent of total consumption 70-80%, continue full and uniform mixing in high-speed mixer, then discharging, and use screw extruder fully to shear dispersion, obtain base material；
S3: adding 0.6-0.1 weight portion firming agent and the remaining organo silane coupling agent for total consumption 20-30% in base material, extruding pelletization after full and uniform mixing, thus obtaining described novel resin composition。
The inventors discovered that, when using preparation method so, it is possible to obtain having the resin combination (being specifically shown in sign data subsequently) of most excellent properties。
3rd aspect, the present invention relates to the described resin combination purposes for preparation engineering plastics。
Owing to the described resin combination of the present invention has good intensity and weatherability, such that it is able to be used for preparing various engineering plastics, for instance for electric appliance casing, machinery plastic components etc.。
In sum, the invention provides a kind of resin combination with good strength and excellent weather resistance and its production and use, described resin combination is by the mutually collaborative of unique compositional selecting, preparation method etc. and promotes, thus having mechanical property and the weather resistance etc. of excellence, such that it is able to be applied in multiple specific field, there is good application potential and industrial production prospect。
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further described。But the purposes of these exemplary embodiments and purpose are only used for enumerating the present invention, not the real protection scope of the present invention is constituted any type of any restriction, more non-protection scope of the present invention is limited thereto。
Preparation example: the preparation of wastewaters with modified calcium sulfate whiskers
A1: calcium sulfate crystal whiskers is cut into the length of 0.3mm, joins in enough dehydrated alcohol, ultrasonic waves for cleaning 25 minutes, filters, and after cleaning, calcium sulfate crystal whiskers deionized water wash 2-3 time, pulls out, fully dry, obtains clean calcium sulfate crystal whiskers；
A2: clean calcium sulfate crystal whiskers is joined in the dehydrated alcohol into its 9 times of quality, (mass ratio of described clean calcium sulfate crystal whiskers and positive isopropyl silicate is 1:0.5 to be slow added into the ethanol solution of positive isopropyl silicate, the mass percent concentration of described positive isopropyl silicate is 25%), stirring reaction 50 minutes, filter, gained whisker deionized water is fully washed 3-4 time, dry, the dried whisker obtained is calcined 35 minutes at 320 DEG C, naturally cool to room temperature, namely obtain described wastewaters with modified calcium sulfate whiskers。
Embodiment 1
S1: according to the weight ratio of 2:1:1, weighs phenol A type epoxy resin, methacrylic acid-butadiene-styrene terpolymer (MBS resin) and polrvinyl chloride, and uses high-speed mixer to carry out full and uniform mixing, obtain 80 parts by weight resin masterbatch；
S2: add 1 weight portion in above-mentioned resin concentrates and prepare the wastewaters with modified calcium sulfate whiskers that example obtains, 1 weight portion stabilizer dimercapto 2-ethyl hexyl ethanoate stannous methide, 3 weight portions toughener MBS terpolymer (MBS), 0.4 weight portion nano carbon black, 3 weight portion thiodipropionic acid dilauryl cinnamic acid esters, 1 weight portion bi-component antioxidant (three (2 for mass ratio 1:1, 4-di-tert-butyl-phenyl) phosphite ester and 1, 3, 5-trimethyl-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) mixture of benzene), 0.8 weight portion adhesive accelerant formula (I) compound, 6 weight portion auxiliary agents (the mass mixing thing such as grade for carboxyethyl cellulose with hydroxyapatite, the granularity of described hydroxyapatite is 100-150 order) and 0.98 weight portion organo silane coupling agent β-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane (for total consumption 1.4 weight portion 70%), continue full and uniform mixing in high-speed mixer, then discharging, and use screw extruder fully to shear dispersion, obtain base material；
S3: add 0.6 weight portion firming agent 3 in base material, 3'-dimethyl-4,4'-diamino-dicyclohexyl methane and remaining be 0.42 weight portion organo silane coupling agent β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane (for total consumption 1.4 weight portion 30%), extruding pelletization after full and uniform mixing, thus obtaining described novel resin composition, by its called after CL1。
Embodiment 2
S1: according to the weight ratio of 2:1:1, weighs phenol A type epoxy resin, methacrylic acid-butadiene-styrene terpolymer (MBS resin) and polrvinyl chloride, and uses high-speed mixer to carry out full and uniform mixing, obtain 80 parts by weight resin masterbatch；
S2: add 0.5 weight portion in above-mentioned resin concentrates and prepare the wastewaters with modified calcium sulfate whiskers that example obtains, 2 weight portion stabilizer dimercapto 2-ethyl hexyl ethanoate stannous methides, 2 weight portions toughener MBS terpolymer (MBS), 0.8 weight portion nano carbon black, 2 weight portion thiodipropionic acid dilauryl cinnamic acid esters, 1.6 weight portion bi-component antioxidant (three (2 for mass ratio 1:2, 4-di-tert-butyl-phenyl) phosphite ester and 1, 3, 5-trimethyl-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) mixture of benzene), 0.5 weight portion adhesive accelerant formula (I) compound, 8 weight portion auxiliary agents (the mass mixing thing such as grade for carboxyethyl cellulose with hydroxyapatite, the granularity of described hydroxyapatite is 100-150 order) and 1.6 weight portion organo silane coupling agent β-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane (for total consumption 2 weight portion 80%), continue full and uniform mixing in high-speed mixer, then discharging, and use screw extruder fully to shear dispersion, obtain base material；
S3: add 1 weight portion firming agent 3 in base material, 3'-dimethyl-4,4'-diamino-dicyclohexyl methane and remaining be 0.4 weight portion organo silane coupling agent β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane (for total consumption 2 weight portion 20%), extruding pelletization after full and uniform mixing, thus obtaining described novel resin composition, by its called after CL2。
Embodiment 3
S1: according to the weight ratio of 2:1:1, weighs phenol A type epoxy resin, methacrylic acid-butadiene-styrene terpolymer (MBS resin) and polrvinyl chloride, and uses high-speed mixer to carry out full and uniform mixing, obtain 80 parts by weight resin masterbatch；
S2: add 0.75 weight portion in above-mentioned resin concentrates and prepare the wastewaters with modified calcium sulfate whiskers that example obtains, 1.5 weight portion stabilizer dimercapto 2-ethyl hexyl ethanoate stannous methides, 2.5 weight portions toughener MBS terpolymer (MBS), 0.6 weight portion nano carbon black, 2.5 weight portion thiodipropionic acid dilauryl cinnamic acid esters, 1.3 weight portion bi-component antioxidant (three (2 for mass ratio 1:1.5, 4-di-tert-butyl-phenyl) phosphite ester and 1, 3, 5-trimethyl-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) mixture of benzene), 0.65 weight portion adhesive accelerant formula (I) compound, 7 weight portion auxiliary agents (the mass mixing thing such as grade for carboxyethyl cellulose with hydroxyapatite, the granularity of described hydroxyapatite is 100-150 order) and 1.35 weight portion organo silane coupling agent β-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane (for total consumption 1.8 weight portion 75%), continue full and uniform mixing in high-speed mixer, then discharging, and use screw extruder fully to shear dispersion, obtain base material；
S3: add 0.8 weight portion firming agent 3 in base material, 3'-dimethyl-4,4'-diamino-dicyclohexyl methane and remaining be 0.45 weight portion organo silane coupling agent β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane (for total consumption 1.8 weight portion 25%), extruding pelletization after full and uniform mixing, thus obtaining described novel resin composition, by its called after CL3。
Comparative example 1-3
Except calcium sulfate crystal whiskers not being modified, (namely only add the calcium sulfate crystal whiskers of identical weight part), sequentially implement comparative example 1-3 respectively with the same procedure with embodiment 1-3, resin combination sequentially called after D1, D2 and the D3 that will obtain。
Comparative example 4-9
Comparative example 4-6: except stabilizer therein is replaced with di-n-butyltin dilaurate, other operation is all constant, thus repeating to implement embodiment 1-3, sequentially obtains comparative example 4-6, resin combination sequentially called after D4, D5 and the D6 that will obtain。
Comparative example 7-9: except stabilizer therein is replaced with trisnonyl phenyl phosphite, other operation is all constant, thus repeating to implement embodiment 1-3, sequentially obtains comparative example 7-9, resin combination sequentially called after D7, D8 and the D9 that will obtain。
Comparative example 10-15
Comparative example 10-12: except toughener therein is replaced with latex powder, other operation is all constant, thus repeating to implement embodiment 1-3, sequentially obtains comparative example 10-12, resin combination sequentially called after D10, D11 and the D12 that will obtain。
Comparative example 13-15: except toughener therein is replaced with poly-epsilon-caprolactone, other operation is all constant, thus repeating to implement embodiment 1-3, sequentially obtains comparative example 13-15, resin combination sequentially called after D13, D14 and the D15 that will obtain。
Comparative example 16-24
Comparative example 16-18: except organo silane coupling agent therein is replaced with methacryloxypropyl trimethoxy silane, other operation is all constant, thus repeating to implement embodiment 1-3, sequentially obtain comparative example 16-18, resin combination sequentially called after D16, D17 and the D18 that will obtain。
Comparative example 19-21: except organo silane coupling agent therein is replaced with phenylaminomethyl triethoxysilane, other operation is all constant, thus repeating to implement embodiment 1-3, sequentially obtain comparative example 19-21, resin combination sequentially called after D19, D20 and the D21 that will obtain。
Comparative example 22-24: except organo silane coupling agent therein is replaced with γ-glycidyl ether oxygen propyl trimethoxy silicane, other operation is all constant, thus repeating to implement embodiment 1-3, sequentially obtain comparative example 22-24, resin combination sequentially called after D22, D23 and the D24 that will obtain。
Comparative example 25-30
Comparative example 25-27: except bi-component antioxidant being replaced the one-component (2 becoming original gross mass, 4-di-tert-butyl-phenyl) outside phosphite ester, other operation is all constant, thus repeating to implement embodiment 1-3, sequentially obtain comparative example 25-27, resin combination sequentially called after D25, D26 and the D27 that will obtain。
Comparative example 28-30: except bi-component antioxidant being replaced the one-component 1 becoming original gross mass, 3,5-trimethyl-2, outside 4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, other operation is all constant, thus repeating to implement embodiment 1-3, sequentially obtain comparative example 28-30, resin combination sequentially called after D28, D29 and the D30 that will obtain。
Comparative example 31-33
Except adhesive accelerant replaces with formula (II) compound, other operation is all constant, thus repeating to implement embodiment 1-3, sequentially obtains comparative example 31-33, resin combination sequentially called after D31, D32 and the D33 that will obtain。
Comparative example 34-39
Comparative example 34-36: except firming agent is replaced with 5-amino-1, outside 3,3-3-methyl cyclohexanol methylamines, other operation is all constant, thus repeating to implement embodiment 1-3, sequentially obtains comparative example 34-36, resin combination sequentially called after D34, D35 and the D36 that will obtain。
Comparative example 37-39: except replacing with outside 4,4'-diamino bicyclic hexyl methane by firming agent, other operation is all constant, thus repeating to implement embodiment 1-3, sequentially obtains comparative example 37-39, resin combination sequentially called after D37, D38 and the D39 that will obtain。
Comparative example 40-42
Except the difference all of organo silane coupling agent of disposable addition (not namely being added with machine silane coupling agent in step s3) in step s 2, other operation is all constant, thus repeating to implement embodiment 1-3, sequentially obtain comparative example 40-42, resin combination sequentially called after D40, D41 and the D42 that will obtain。
Comparative example 43-45
Except the difference all of organo silane coupling agent of disposable addition (not namely being added with machine silane coupling agent in step s 2) in step s3, other operation is all constant, thus repeating to implement embodiment 1-3, sequentially obtain comparative example 43-45, resin combination sequentially called after D43, D44 and the D45 that will obtain。
Performance test
In order to carry out corresponding performance test, resin combination embodiment and comparative example obtained carries out injection mo(u)lding, thus obtaining test sample。
1, the mensuration of hot strength and bending strength
Test sample carries out the mensuration of hot strength and bending strength according to standard GB/T/T1040-92, and concrete outcome is shown in table 1 below。
The intensity of the different sample of table 1.
As can be seen here: 1, when calcium sulfate crystal whiskers does not carry out the inventive method modified, cause that intensity has and significant reduce (see D1-D3)；2, when changing the kind of toughener (see D10-D15), organo silane coupling agent (see D16-D24), adhesive accelerant (see D31-D33) and firming agent (see D34-D39), all cause that hot strength has significant reduction, even if adopting (II) compound very similar with adhesive accelerant (I) compound, or adopt and firming agent 3,3'-dimethyl-4,4'-diamino-dicyclohexyl methane very similar 4,4'-diamino bicyclic hexyl methane, also leads to hot strength and has obvious reduction。
All these, all demonstrates the selection right and wrong for these concrete components it will be apparent that and can obtain beyond thought promotion and synergy each other。
It can also be seen that when organo silane coupling agent is in preparation method, fashionable when adding in batches step by step in step S2 and S3 as described herein, it is possible to obtain best technique effect。And when all in S2 disposable adding fashionable or all disposable in S3 add fashionable (see D40-D45), also lead to intensity had and significantly reduce, reason should be ought add in batches fashionable, organo silane coupling agent first can play initial coupling in step s 2, and can again carry out degree of depth coupling when mixing again in step s3, such that it is able to obtain best coupling effect, create intensity the most excellent。
2, weatherability test
The resin combination injection mo(u)lding that above-described embodiment and comparative example prepare is obtained plastic sheet, the mensuration of hot strength is first carried out according to GB/T1040-92, and record respective stretching data (namely the concrete data in upper table 1), then according to GB/T16422.2 carries out xenon lamp aging weather resistant experiment test, after test 500 hours, observe its configuration of surface, and again measure its hot strength, investigating its aging further, result is shown in table 2 below。
Table 2. weatherability test result
Wherein, for " configuration of surface ", " √ √ " represents Apparently in Good Order& Condition, with original state zero difference；" √ " represents that surface has bubbling, powder, aging layer or crackle to occur, compared with original state, hence it is evident that can be seen that there is surface aging phenomenon, "×" represents that there is serious degree of aging on surface, will more be inferior to " √ "。For hot strength reduction rate (%), reduction rate is more little, then prove that degree of aging is more light, and reduction rate is more big, then prove that degree of aging is more serious, thus original hot strength cannot be kept。
As can be seen here, the present invention there is particular combination and resin combination that specific preparation method obtains has the weatherability of excellence, and it is unmodified when changing some component such as calcium sulfate crystal whiskers therein, stabilizer, toughener, antioxidant, when adhesive accelerant and firming agent, all will cause that weatherability has significant reduction, when especially bi-component antioxidant being replaced with one-component (see D25-D30), and when changing firming agent kind (see D34-D39), all will cause that weatherability has significantly to deteriorate, this proves to play beyond thought collaborative facilitation effect between bi-component antioxidant, and the kind demonstrating firming agent has significant beyond thought impact for weatherability。
It can also be seen that, in the preparation method of the present invention, organo silane coupling agent step by step, add in batches, affect weatherability performance equally, although failing to find out configuration of surface and deteriorating to some extent, but the hot strength of reality reduces, and to show that it still has a degree of aging。
In sum, the invention provides a kind of resin combination with good strength and excellent weather resistance and its production and use, described resin combination is by the mutually collaborative of unique compositional selecting, preparation method etc. and promotes, thus having mechanical property and the weather resistance etc. of excellence, such that it is able to be applied in multiple specific field, there is good application potential and industrial production prospect。
Should be appreciated that the purposes of these instantiations is merely to illustrate the present invention and is not intended to limit the scope of the invention。In addition; it is also contemplated that; after the technology contents having read the present invention, the present invention can be made various change, amendment and/or modification by those skilled in the art, and all these equivalent form of value falls within the application appended claims protection defined equally。
Claims (10)
1. a novel resin composition, described novel resin composition includes resin concentrates, wastewaters with modified calcium sulfate whiskers, stabilizer, toughener, nano carbon black, organo silane coupling agent, thiodipropionic acid dilauryl cinnamic acid ester, bi-component antioxidant, adhesive accelerant, firming agent and auxiliary agent。
2. a kind of novel resin composition as claimed in claim 1, it is characterised in that: with parts by weight, described novel resin composition includes following component:
3. a kind of novel resin composition as claimed in claim 1 or 2, it is characterised in that: described resin concentrates is the mixture of bisphenol A type epoxy resin, methacrylic acid-butadiene-styrene terpolymer (MBS resin) and polrvinyl chloride。Wherein, the weight ratio of bisphenol A type epoxy resin, methacrylic acid-butadiene-styrene terpolymer (MBS resin) and polrvinyl chloride is 2:1:1。
4. a kind of novel resin composition as described in any one of claim 1-3, it is characterised in that: described wastewaters with modified calcium sulfate whiskers is to prepare according to the preparation method comprised the steps:
A1: calcium sulfate crystal whiskers is cut into the length of 0.2-0.5mm, joins in dehydrated alcohol, ultrasonic waves for cleaning 20-30 minute, filters, and after cleaning, calcium sulfate crystal whiskers deionized water wash 2-3 time, pulls out, fully dry, obtains clean calcium sulfate crystal whiskers；
A2: cleaning calcium sulfate crystal whiskers is joined in dehydrated alcohol, it is slow added into the ethanol solution of positive isopropyl silicate, stirring reaction 40-60 minute, filter, gained whisker deionized water is fully washed 3-4 time, dry, the dried whisker obtained is calcined 30-40 minute at 300-340 DEG C, naturally cool to room temperature, namely obtain described wastewaters with modified calcium sulfate whiskers。
5. a kind of novel resin composition as described in any one of claim 1-4, it is characterized in that: any in di-n-butyltin dilaurate, dimercapto 2-ethyl hexyl ethanoate stannous methide or trisnonyl phenyl phosphite of described stabilizer, it is most preferred that for dimercapto 2-ethyl hexyl ethanoate stannous methide。
6. a kind of novel resin composition as described in any one of claim 1-5, it is characterized in that: described organo silane coupling agent is methacryloxypropyl trimethoxy silane, phenylaminomethyl triethoxysilane, β-(3,4-epoxycyclohexyl) any one in ethyl trimethoxy silane or γ-glycidyl ether oxygen propyl trimethoxy silicane, it most preferably is β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane。
7. a kind of novel resin composition as described in any one of claim 1-6, it is characterized in that: described bi-component antioxidant is the three (2 of mass ratio 1:1-2,4-di-tert-butyl-phenyl) phosphite ester and 1,3,5-trimethyl-2, the mixture of 4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene。
8. a kind of novel resin composition as claimed in claim 7, it is characterised in that: described adhesive accelerant is following formula (I) compound or (II) compound,
It most preferably is described formula (I) compound。
9. the preparation method of a kind of novel resin composition described in any one of claim 1-8, described preparation method comprises the steps:
S1: according to the weight ratio of 2:1:1, weigh phenol A type epoxy resin, methacrylic acid-butadiene-styrene terpolymer (MBS resin) and polrvinyl chloride, and use high-speed mixer to carry out full and uniform mixing, obtain 80-90 parts by weight resin masterbatch；
S2: add the part by weight modified calcium sulfate crystal whiskers of 0.5-1,1-2 weight portion stabilizer, 2-3 weight portion toughener, 0.4-0.8 weight portion nano carbon black, 2-3 weight portion thiodipropionic acid dilauryl cinnamic acid ester, 1-1.6 weight portion bi-component antioxidant, 0.5-0.8 weight portion adhesive accelerant, 6-8 weight portion auxiliary agent in above-mentioned resin concentrates and be the organo silane coupling agent of total consumption 70-80%, continue full and uniform mixing in high-speed mixer, then discharging, and use screw extruder fully to shear dispersion, obtain base material；
S3: adding 0.6-0.1 weight portion firming agent and the remaining organo silane coupling agent for total consumption 20-30% in base material, extruding pelletization after full and uniform mixing, thus obtaining described novel resin composition。
10. a kind of novel resin composition as described in any one of claim 1-8 is used for the purposes of preparation engineering plastics。
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Cited By (2)
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| CN110724363A (en) * | 2019-09-05 | 2020-01-24 | 天长市宏福电子有限公司 | Efficient wear-resistant sensor shell material and preparation method thereof |
| CN116574359A (en) * | 2023-06-20 | 2023-08-11 | 深圳市辉亚新材料科技有限公司 | Impact-resistant modified epoxy resin and preparation process thereof |
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