CN108976378A - A kind of flame retardant type compound resin - Google Patents
A kind of flame retardant type compound resin Download PDFInfo
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- CN108976378A CN108976378A CN201810336538.8A CN201810336538A CN108976378A CN 108976378 A CN108976378 A CN 108976378A CN 201810336538 A CN201810336538 A CN 201810336538A CN 108976378 A CN108976378 A CN 108976378A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
- C08G18/582—Epoxy resins having halogens
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1405—Polycondensates modified by chemical after-treatment with inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1494—Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
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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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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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
- C08L2201/02—Flame or fire retardant/resistant
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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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Abstract
The present invention relates to compound resin technical fields, more particularly to a kind of flame retardant type compound resin, the flame retardant type compound resin is made of raw material, on the basis of 100 parts by weight of epoxy resin, the raw material includes the substance of following parts by weight: 100 parts by weight of epoxy resin, 5~20 parts by weight of chlorine source, 10~40 parts by weight of polyether polyol, 12~48 parts by weight of isocyanates, 5~12 parts by weight of catalyst, 3~15 parts by weight of reinforcing fiber, 1~10 parts by weight of chain extender, 2~8 parts by weight of surfactant, 10~15 parts by weight of curing agent, 80~200 parts by weight of organic solvent.The present invention uses chlorine source to be modified epoxy resin first, improve the flame retarding and smoke suppressing properties of epoxy resin, by the reaction was continued with polyether polyol, isocyanates in modified epoxy resin, generate the compound resin of epoxy resin and polyurethane, by the synergistic effect of the two, make compound resin that there is high tenacity, high intensity and excellent flame retardant property.
Description
Technical field
The present invention relates to compound resin technical fields, and in particular to a kind of flame retardant type compound resin.
Background technique
As world economy fast development and people's lives are continuously improved, auto industry is rapidly developed, and Automotive day is new
The moon is different, and vehicle is constantly updated.Requirement of the people to car is not only the appearance of beautiful design, and is more concerned with upholstery
Comfort, globality, functionality.It is required that these materials are not only have the spies such as heat-insulated, noise reduction, shockproof, fire-retardant, both artistic and practical
Property, but also the structural door plate material and other structural interior materials for requiring some functional components such as CD case, instrument box etc.
It all has following requirement: (1) there is certain shock resistance, or even when car is when running at high speed and colliding, function
The machinery of energy property component is still able to maintain normal operation with instrument function.
Since epoxy resin-matrix compound resin has the excellent objects such as good insulating, intensity height, the low, chemical resistance of specific gravity
Physicochemical performance, while the characteristics of but also with easy processing, therefore epoxy resin-matrix compound resin occupies weight in automobile interior decoration field
The status wanted.In existing epoxy resin-matrix compound resin, use glass fabric or glass fiber felt for its reinforcement；Asphalt mixtures modified by epoxy resin
Rouge is bromination type epoxy resin.Have the following disadvantages: (1) due to 2 times that the density of glass fabric, glass fiber felt is epoxy resin
More than, therefore the specific gravity of compound resin is largely increased, and with the increase of above-mentioned proportion of filler, compound resin
Brittleness increases, impact resistance decline.(2) although brominated epoxy resin has good flame resistance, it has become daily
The pollutant spread everywhere in environment, and harmful substance can be discharged in burning and heating process, it pollutes environment and endangers people
Class health.European Union on July 1 in 2006 is even more to implement WEEE and two parts of RoHS instructions, is forbidden in electric equipment products
Using the harmful substances such as polybrominated biphenyls (PBB) and polybrominated diphenyl ethers (PBDE), indicate that electronic apparatus enters the Bromineless environment friendly epoch.
For this reason, it may be necessary to which it is imperative to develop low-density, high intensity and environmentally friendly bromine-free flame-retardant type compound resin.
Summary of the invention
It is of the existing technology the purpose of the invention is to overcome the problems, such as, a kind of flame retardant type compound resin is provided, it has
Have the characteristics that density is low, intensity is high, good flame retardation effect and environmentally friendly.
To achieve the goals above, the present invention provides a kind of flame retardant type compound resin, and the flame retardant type compound resin is by original
Feed composition is made, on the basis of 100 parts by weight of epoxy resin, the feedstock composition include: 100 parts by weight of epoxy resin,
5~20 parts by weight of chlorine source, 10~40 parts by weight of polyether polyol, 12~48 parts by weight of isocyanates, 5~12 weight of catalyst
Part, 3~15 parts by weight of reinforcing fiber, 1~10 parts by weight of chain extender, 2~8 parts by weight of surfactant, 10~15 weight of curing agent
Measure part, 80~200 parts by weight of organic solvent.
Through the above technical solutions, the present invention uses chlorine source to be modified epoxy resin first, in asphalt mixtures modified by epoxy resin fat chain
The fire-retardant factor is introduced, the flame retarding and smoke suppressing properties of epoxy resin are improved, will be continued in modified epoxy resin with polyether polyol
Reaction can relay continuous introducing polyether polyols alcohol groups in asphalt mixtures modified by epoxy resin fat chain, and polyether polyols alcohol groups and isocyanates continue anti-
The compound resin of epoxy resin and polyurethane should further be generated, in the compound resin, epoxy resin and polyurethane form sky
Between network structure, therefore the compound resin had not only had a rigid structure of epoxy resin, but also the elastic construction with polyurethane, led to
The synergistic effect for crossing the two makes compound resin have high tenacity, high intensity and excellent flame retardant property.
Specific embodiment
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.
In order to improve the intensity of resin and obtain lightweight and environmental-friendly flame retardant type compound resin, mention in the present invention
A kind of flame retardant type compound resin is supplied, the flame retardant type compound resin is made of raw material, using 100 parts by weight of epoxy resin as base
Standard, the feedstock composition include: 100 parts by weight of epoxy resin, 5~20 parts by weight of chlorine source, 10~40 weight of polyether polyol
Part, 12~48 parts by weight of isocyanates, 5~12 parts by weight of catalyst, 3~15 parts by weight of reinforcing fiber, 1~10 weight of chain extender
Part, 2~8 parts by weight of surfactant, 10~15 parts by weight of curing agent, 80~200 parts by weight of organic solvent.
In the present invention, chlorine source can be modified epoxy resin, and the fire-retardant factor is introduced in asphalt mixtures modified by epoxy resin fat chain, improve ring
The flame retarding and smoke suppressing properties of oxygen resin, then by epoxy resin, the reaction was continued with polyether polyol, can relay in asphalt mixtures modified by epoxy resin fat chain
Continuous to introduce polyether polyols alcohol groups, the reaction was continued further generates epoxy resin and poly- ammonia for polyether polyols alcohol groups and isocyanates
The compound resin of ester, epoxy resin and polyurethane form spacial framework, therefore the compound resin in the compound resin
Not only the elastic construction with the rigid structure of epoxy resin, but also with polyurethane makes compound resin by the synergistic effect of the two
With high tenacity, high intensity and excellent flame retardant property.
In order to optimize the mechanical property of flame retardant type compound resin, under preferable case, using 100 parts by weight of epoxy resin as base
Standard, the feedstock composition include: 100 parts by weight of epoxy resin, 8~16 parts by weight of chlorine source, 15~30 weight of polyether polyol
Part, 18~40 parts by weight of isocyanates, 8~10 parts by weight of catalyst, 5~12 parts by weight of reinforcing fiber, 2~8 weight of chain extender
Part, 2~8 parts by weight of surfactant, 10~15 parts by weight of curing agent, 120~150 parts by weight of organic solvent.
In the present invention, in order to improve the flame retardant property of flame retardant type compound resin, under preferable case, the epoxy resin and chlorine
The mass ratio in source is 1:(0.1~0.15).
In the present invention, under preferable case, the epoxy resin be selected from melamine epoxy resin, phenol aldehyde type epoxy resin,
Bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bis-phenol H-type epoxy resin, multifunctional shrink are sweet
At least one of oily ether type epoxy, multifunctional glycidyl amine type epoxy resin.
In order to improve the content of chlorine element in epoxy resin, under preferable case, chlorine source is selected from phosphoryl chloride phosphorus oxychloride, phosphoric
At least one of phosphorus, phosphorus trichloride and chlorine dioxide.
In the present invention, catalyst can be catalyzed reacting for chlorine source and epoxy resin, and under preferable case, the catalyst is selected from
At least one of triethyl benzyl ammonia chloride, triethylbenzyl ammonium bromide and N, N- dimethyl Bian amine.
According to the present invention, the main function of reinforcing fiber is the intensity for improving compound resin, under preferable case, the enhancing
Fiber be selected from calcium sulfate crystal whiskers, alumina whisker, silicon carbide whisker, carbonization boron whisker, zirconium dioxide whisker, aluminium nitride whisker,
At least one of ZnOw, magnesia crystal whisker, magnesium sulfate crystal whisker and silicon nitride crystal whisker.In order to further increase compound tree
The intensity of rouge, under preferable case, the diameter of the reinforcing fiber is 50~150nm, and length is 3~12 μm.
In the present invention, on the one hand the polyether polyol can carry out recombination reaction with epoxy resin, by the epoxy of rigidity
Resin long-chain is introduced into polyether polyol, and on the other hand, the polyether polyol can be reacted with isocyanates generates polyurethane,
To which polyurethane and epoxy resin compound resin be prepared.Under preferable case, the polyether polyol is selected from polyether Glycols
And/or polyether-tribasic alcohol, more specifically polyoxypropyleneglycol, polytetrahydrofuran diol, tetrahydrofuran-propylene oxide copolymerization two
At least one of pure and mild polypropylene oxide triol.
According to the present invention, isocyanates can be reacted with polyether polyol, generation polyurethane, described different under preferable case
Cyanate is selected from toluene di-isocyanate(TDI), isophorone diisocyanate, methyl diphenylene diisocyanate, dicyclohexyl methyl hydride
At least one of diisocyanate, hexamethylene diisocyanate, lysine diisocyanate.
In the case of, according to the invention it is preferred to, the chain extender in aliphatic diol and aromatic diol at least one
Kind.Wherein the aliphatic diol is selected from ethylene glycol, 1,3 butylene glycol, 1,10- certain herbaceous plants with big flowers glycol, 1,4- cyclohexanediol, 1,8- pungent two
Alcohol, neopentyl glycol, 2- methyl-1,3-propanediol, 2,4- diethyl -1,5- pentanediol and 3- methyl-1, in 5- pentanediol extremely
Few one kind；Wherein the aromatic diol is selected from hydroquinone double hydroxyethyl ether and/or resorcinol double hydroxyethyl ether.
In the case of, according to the invention it is preferred to, the surfactant is selected from dodecyl alcohol polyoxyethylene ether sodium sulfate, ten
Dialkyl group ammonium sulfate, lauryl sodium sulfate, dodecyl benzene sulfonic acid, sodium secondary alkyl sulfonate, fatty alcohol sodium isethionate, N-
Lauroyl musculamine acid sodium, coconut acyl methyl taurine sodium, α-sodium olefin sulfonate, in dodecyl phosphide ester triethanolamine at least
It is a kind of.
In the case of, according to the invention it is preferred to, the organic solvent is selected from acetone, n,N-Dimethylformamide, N- methyl pyrrole
Pyrrolidone, DMAC N,N' dimethyl acetamide, dimethyl acetamide, methylene chloride, triethyl phosphate, acetone, chloroform, toluene,
At least one of ethyl alcohol, acetic acid, ethyl acetate, formic acid, chloroform, tetrahydrofuran, atoleine and dimethyl sulfoxide.
In the case of, according to the invention it is preferred to, the curing agent is selected from ethylenediamine, hexamethylene diamine, methyl cyclohexyl diamine, Isosorbide-5-Nitrae-fourth
Diamines, 1,5- pentanediamine, 2- methyl-1,5- pentanediamine, 2- butyl -2- ethyl -1,5- pentanediamine, 1,6- hexamethylene diamine, 2,2,4-
Trimethylhexane diamine, 2,4,4- trimethylhexane diamine, 1,8- octamethylenediamine, 2- methyl-1,8- octamethylenediamine, 1,9-nonamethylene diamine, 1,10-
Decamethylene diamine, 1,11- hendecane diamines, 1,12- dodecamethylene diamine, 1,13- tridecane diamine, 1,14- tetradecane diamines, 1,15-
Pentadecane diamines, 2- methyl -2,4-PD, 1,16- hexadecane diamines and 1,18-1,14- octadecamethylene diamine, dimethyl sulphur-based first
At least one of phenylenediamine.
Meanwhile a kind of preparation method of flame retardant type compound resin according to the present invention being also provided in the present invention, including with
Lower step:
(1) chlorine source, epoxy resin and catalyst are uniformly mixed in first part's organic solvent, then 80~120
It is heated to reflux 1~8h at DEG C, obtains mixed system 1；
(2) the pure and mild first part's chain extender of polyether polyols is added into mixed system 1, is then reacted at 60~80 DEG C
0.5~5h obtains mixed system 2；
(3) isocyanates, reinforcing fiber, second part chain extender, surfactant and second are added into mixed system 2
Part organic solvent after reacting 2~6h at 80~100 DEG C, is added curing agent, after solidified forming, obtains the compound tree of flame retardant type
Rouge.
In the case of, according to the invention it is preferred to, the weight ratio of first part's organic solvent and second part organic solvent
For (1.66~5): 1.
In the case of, according to the invention it is preferred to, the weight ratio of first part's chain extender and second part chain extender is (1
~3): 1.
In the present invention, reacted under the conditions of first by chlorine source and epoxy resin existing for the catalyst, to epoxy resin
It is modified, fire-retardant group-chloro is introduced in asphalt mixtures modified by epoxy resin fat chain, to improve the flame retardant property of epoxy resin, then again will
Epoxy resin is reacted with polyether polyol, epoxy resin surface introduce polyether polyols alcohol groups, and make the group continue with it is different
Cyanate is reacted, and the compound resin of epoxy resin and polyurethane is obtained, which has light weight, intensity high, tough
The feature that property is good, flame retardant property is good, has potential application on the interior trim of automobile.
In the present invention, by reinforcing fiber being added, reinforcing fiber can be made by resin during preparing compound resin
Cladding, on the one hand, improve stability of the reinforcing fiber in compound resin, on the other hand, also improve reinforcing fiber multiple
The uniformity in resin.
The present invention also provides a kind of automotive upholsteries, the compound tree including fabric and with the fabric injection molding connection
Rouge, the compound resin use flame retardant type compound resin according to the present invention.
The present invention does not require the type of fabric particularly, can be in the prior art for the common fabric of interior trim.
In a preferred embodiment of the invention, the fabric is selected from least one of cotton, fiber crops, terylene, spandex or nylon.
In yet another embodiment of the present invention, the automotive upholstery the preparation method is as follows:
(1) prepared by compound resin: the compound resin uses flame retardant type compound resin according to the present invention, preparation
Method is referring to the present invention previously with regard to the description of the preparation method of flame retardant type compound resin；
(2) prepared by automotive upholstery: fabric and flame retardant type compound resin being placed in mold, injection molding simultaneously demoulds, and obtains
To automotive upholstery.
The present invention does not have special requirement to the injection molding process of automotive upholstery, can be asphalt mixtures modified by epoxy resin in the prior art
The common Shooting Technique of rouge, under preferable case, the technique of the injection molding are as follows: clamp force 600-800T, injection pressure 2-
4bar, pressure switch 2-4bar, injection time 3-5s, dwell time 13-16s.
The present invention will be described in detail by way of examples below.In following embodiment, various kinds is tested using drainage
The density of product.According to the elongation at break and tensile strength of the method test each sample of GB/T1040.1-2006.According to GB/
The impact flexibility of the method test each sample of T1451-2005.Each sample is tested according to the combustibility method of GB/T2406-199
Oxygen index (OI).
Embodiment 1
(1) prepared by compound resin:
By 12g phosphorus pentachloride, 100g phenol aldehyde type epoxy resin and 10g triethyl benzyl ammonia chloride in 100g dimethyl sulfoxide
In be uniformly mixed, be then heated to reflux 6h at 100 DEG C, obtain mixed system 1；
25g polytetrahydrofuran diol and 4g ethylene glycol are added into mixed system 1, then reacts 2h at 75 DEG C, obtains
Mixed system 2；
30g isocyanates, 10g alumina whisker (diameter 80nm, length are 5 μm), 2g second are added into mixed system 2
After reacting 4h at 90 DEG C, 12g 2 is added in glycol, 5g dodecyl alcohol polyoxyethylene ether sodium sulfate and 50g dimethyl sulfoxide,
4,4- trimethylhexane diamines after solidified forming, obtain flame retardant type compound resin.
(2) prepared by automotive upholstery: polyester fabric and flame retardant type compound resin being placed in mold, are in clamp force
700T, injection pressure 3bar, pressure switch 3bar, and injection time 5s, the dwell time is injection molding under conditions of 15s and takes off
Mould obtains automotive upholstery.
Embodiment 2
(1) prepared by compound resin:
8g phosphoryl chloride phosphorus oxychloride, 100g bisphenol A type epoxy resin and 10g triethylbenzyl ammonium bromide are mixed in 120g ethyl acetate
It closes uniformly, is then heated to reflux 4h at 100 DEG C, obtains mixed system 1；
15g polytetrahydrofuran diol and 1.5g 2- methyl-1,3-propanediol, then at 70 DEG C are added into mixed system 1
Lower reaction 3h, obtains mixed system 2；
18g isocyanates, 5g aluminium nitride whisker (diameter 80nm, length are 8 μm), 0.5g are added into mixed system 2
After reacting 4h at 80 DEG C, 12g 1 is added in 2- methyl-1,3-propanediol, 3g ammonium lauryl sulfate and 30g ethyl acetate,
14- tetradecane diamines after solidified forming, obtains flame retardant type compound resin.
(2) prepared by automotive upholstery: spandex face fabric and flame retardant type compound resin being placed in mold, are in clamp force
750T, injection pressure 4bar, pressure switch 4bar, and injection time 3s, the dwell time is injection molding under conditions of 14s and takes off
Mould obtains automotive upholstery.
Embodiment 3
(1) prepared by compound resin:
By 16g phosphorus trichloride, 100g bisphenol f type epoxy resin and 8g triethylbenzyl ammonium bromide in 100g dimethylacetamide
It is uniformly mixed in amine, is then heated to reflux 4h at 120 DEG C, obtains mixed system 1；
30g polyoxypropyleneglycol and 5g 1,3-BDO are added into mixed system 1, then reacts 1h at 80 DEG C,
Obtain mixed system 2；
40g isocyanates, 12g alumina whisker (diameter 100nm, length are 5 μm), 3g are added into mixed system 2
After reacting 3h at 95 DEG C, 10g dimethyl sulphur-based is added in 1,3-BDO, 6g dodecyl benzene sulfonic acid and 20g dimethyl acetamide
Toluenediamine after solidified forming, obtains flame retardant type compound resin.
(2) prepared by automotive upholstery: nylon facing material and flame retardant type compound resin being placed in mold, are in clamp force
650T, injection pressure 4bar, pressure switch 3bar, and injection time 5s, the dwell time is injection molding under conditions of 15s and takes off
Mould obtains automotive upholstery.
Embodiment 4
(1) prepared by compound resin:
20g phosphorus pentachloride, 100g melamine epoxy resin and 5g triethyl benzyl ammonia chloride are mixed in 50g acetone
Uniformly, it then is heated to reflux 1h at 120 DEG C, obtains mixed system 1；
40g polyoxypropyleneglycol and 0.5g Isosorbide-5-Nitrae-cyclohexanediol are added into mixed system 1, it is then anti-at 60 DEG C
5h is answered, mixed system 2 is obtained；
48g isocyanates, 3g silicon carbide whisker (diameter 50nm, length are 3 μm), 0.5g are added into mixed system 2
After reacting 2h at 100 DEG C, 12g 2,4,4- tri- is added in Isosorbide-5-Nitrae-cyclohexanediol, 2g coconut acyl methyl taurine sodium and 30g acetone
Methyl hexamethylene diamine after solidified forming, obtains flame retardant type compound resin.
(2) prepared by automotive upholstery: spandex face fabric and flame retardant type compound resin being placed in mold, are in clamp force
800T, injection pressure 2bar, pressure switch 2bar, and injection time 5s, the dwell time is injection molding under conditions of 13s and takes off
Mould obtains automotive upholstery.
Embodiment 5
(1) prepared by compound resin:
By 5g phosphorus trichloride, 100g bis-phenol H-type epoxy resin and 12g N, N- dimethyl Bian amine in 150g tetrahydrofuran
It is uniformly mixed, is then heated to reflux 8h at 80 DEG C, obtains mixed system 1；
The pure and mild 7g benzenediol double hydroxyethyl ether of 10g polypropylene oxide three is added into mixed system 1, it is then anti-at 80 DEG C
0.5h is answered, mixed system 2 is obtained；
12g isocyanates, 15g silicon nitride crystal whisker (diameter 150nm, length are 12 μm), 3g are added into mixed system 2
After reacting 6h at 80 DEG C, 15g 2 is added in benzenediol double hydroxyethyl ether, 8g N- lauroyl musculamine acid sodium and 50g tetrahydrofuran,
2,4- trimethylhexane diamines after solidified forming, obtain flame retardant type compound resin.
(2) prepared by automotive upholstery: nylon facing material and flame retardant type compound resin being placed in mold, are in clamp force
600T, injection pressure 4bar, pressure switch 4bar, and injection time 3s, the dwell time is injection molding under conditions of 16s and takes off
Mould obtains automotive upholstery.
Comparative example 1
According to the method for embodiment 1, unlike, phosphorus pentachloride is not added in the preparation of flame retardant type compound resin.
Comparative example 2
According to the method for embodiment 1, it unlike, in the preparation of flame retardant type compound resin, does not contain step (2), it is specific to walk
It is rapid as follows:
(1) prepared by compound resin:
By 12g phosphorus pentachloride, 100g phenol aldehyde type epoxy resin and 10g triethyl benzyl ammonia chloride in 50g dimethyl sulfoxide
In be uniformly mixed, be then heated to reflux 6h at 100 DEG C, obtain mixed system 1；
25g polytetrahydrofuran diol, 30g isocyanates, 10g alumina whisker are added into mixed system 1, and (diameter is
80nm, length are 5 μm), 6g ethylene glycol, 5g dodecyl alcohol polyoxyethylene ether sodium sulfate and 100g dimethyl sulfoxide, at 90 DEG C
After lower reaction 4h, 2,4,4- trimethylhexane diamine of 12g is added, after solidified forming, obtains flame retardant type compound resin.
(2) the preparation method is the same as that of Example 1 for automotive upholstery.
Comparative example 3
According to the method for embodiment 1, unlike, reinforcing fiber is not added in the preparation of flame retardant type compound resin.
Comparative example 4
Epoxy resin is directly uniformly mixed in cutter with polyurethane resin, obtains compound resin.
The performance table of each product in 1 Examples 1 to 5 of table and comparative example 1~4
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (9)
1. a kind of flame retardant type compound resin, which is characterized in that the flame retardant type compound resin is made of feedstock composition, with epoxy
On the basis of 100 parts by weight of resin, the feedstock composition includes: 100 parts by weight of epoxy resin, 5~20 parts by weight of chlorine source, polyethers
10~40 parts by weight of polyalcohol, 12~48 parts by weight of isocyanates, 5~12 parts by weight of catalyst, 3~15 weight of reinforcing fiber
Part, 1~10 parts by weight of chain extender, 2~8 parts by weight of surfactant, 10~15 parts by weight of curing agent, organic solvent 80~200
Parts by weight.
2. flame retardant type compound resin according to claim 1, wherein on the basis of 100 parts by weight of epoxy resin, the original
Feed composition includes: 100 parts by weight of epoxy resin, 8~16 parts by weight of chlorine source, 15~30 parts by weight of polyether polyol, isocyanic acid
18~40 parts by weight of ester, 8~10 parts by weight of catalyst, 5~12 parts by weight of reinforcing fiber, 2~8 parts by weight of chain extender, surface are living
2~8 parts by weight of property agent, 10~15 parts by weight of curing agent, 120~150 parts by weight of organic solvent.
3. flame retardant type compound resin according to claim 2, wherein the mass ratio in the epoxy resin and chlorine source is 1:
(0.1~0.15).
4. flame retardant type compound resin according to claim 1, wherein the epoxy resin is selected from melamine epoxy tree
Rouge, phenol aldehyde type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bis-phenol H-type epoxy
At least one of resin, polyfunctional glycidyl ether's type epoxy resin, multifunctional glycidyl amine type epoxy resin.
5. flame retardant type compound resin according to claim 1 or 2, wherein chlorine source be selected from phosphoryl chloride phosphorus oxychloride, phosphorus pentachloride,
At least one of phosphorus trichloride and chlorine dioxide.
6. flame retardant type compound resin according to claim 1 or 2, wherein the catalyst is selected from triethylbenzyl chlorination
At least one of ammonium, triethylbenzyl ammonium bromide and N, N- dimethyl Bian amine.
7. flame retardant type compound resin according to claim 1 or 2, wherein the reinforcing fiber is selected from calcium sulfate crystal whiskers, oxygen
Change al whisker, silicon carbide whisker, carbonization boron whisker, zirconium dioxide whisker, aluminium nitride whisker, ZnOw, magnesia crystal whisker,
At least one of magnesium sulfate crystal whisker and silicon nitride crystal whisker.
8. flame retardant type compound resin according to claim 7, wherein the diameter of the reinforcing fiber is 50~150nm, long
Degree is 3~12 μm.
9. flame retardant type compound resin according to claim 1 or 2, wherein the polyether polyol is selected from polyether Glycols
And/or polyether-tribasic alcohol.
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| CN201810336538.8A CN108976378A (en) | 2018-04-16 | 2018-04-16 | A kind of flame retardant type compound resin |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897140A (en) * | 2014-04-11 | 2014-07-02 | 合肥工业大学 | Epoxy resin modified polyurethane grouting and reinforcing material and preparation method thereof |
| CN105176066A (en) * | 2015-09-30 | 2015-12-23 | 安徽省思维新型建材有限公司 | Heat-resistant and flame-retardant polyurethane foam |
| CN107619461A (en) * | 2017-09-06 | 2018-01-23 | 绵阳旺通科技有限公司 | A kind of high-strength polyurethane flame-retardant thermal insulation material and preparation method thereof |
-
2018
- 2018-04-16 CN CN201810336538.8A patent/CN108976378A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897140A (en) * | 2014-04-11 | 2014-07-02 | 合肥工业大学 | Epoxy resin modified polyurethane grouting and reinforcing material and preparation method thereof |
| CN105176066A (en) * | 2015-09-30 | 2015-12-23 | 安徽省思维新型建材有限公司 | Heat-resistant and flame-retardant polyurethane foam |
| CN107619461A (en) * | 2017-09-06 | 2018-01-23 | 绵阳旺通科技有限公司 | A kind of high-strength polyurethane flame-retardant thermal insulation material and preparation method thereof |
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Application publication date: 20181211 |