CN103450636A - Flame-retardant epoxy resin/lignin/organosilicone composite material and preparation method thereof - Google Patents

Flame-retardant epoxy resin/lignin/organosilicone composite material and preparation method thereof Download PDF

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CN103450636A
CN103450636A CN2013103628751A CN201310362875A CN103450636A CN 103450636 A CN103450636 A CN 103450636A CN 2013103628751 A CN2013103628751 A CN 2013103628751A CN 201310362875 A CN201310362875 A CN 201310362875A CN 103450636 A CN103450636 A CN 103450636A
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epoxy resin
xylogen
epoxy
fire
silane
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CN103450636B (en
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马松琪
樊利波
刘小青
朱锦
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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Abstract

The invention belongs to the field of high polymer materials, and discloses a flame-retardant epoxy resin/lignin/organosilicone composite material and a preparation method thereof. The composite material is prepared by mixing and curing the following active ingredients in parts by mass: 100 parts of epoxy resin, 5-100 parts of lignin, 1-100 parts of epoxy-group organosilicone hybrid, 5-150 parts of curing agent, and 0-6 parts of curing accelerator. Compared with the traditional epoxy resin/lignin composite material, the flame-retardant epoxy resin/lignin/organosilicone composite material disclosed by the invention is more excellent in mechanical property, and has excellent flame retardance property.

Description

A kind of fire-retardant epoxy resin/xylogen/organosilicon matrix material and preparation method thereof
Technical field
The present invention relates to polymeric material field, be specifically related to a kind of fire-retardant epoxy resin/xylogen/organosilicon matrix material and preparation method thereof.
Background technology
Xylogen is that occurring in nature content is only second to cellulosic second largest renewable resources.In paper industry, can produce a large amount of xylogen, no matter be with the paper mill waste liquid enter river course or concentrated after burn, all cause the significant wastage of resource and environment produced to serious pollution.Develop Liginon Resource, not only be conducive to reduce the consumption to the petrochemical industry resource, also be conducive to reduce the pollution to environment simultaneously.
In field of polymer technology, particularly in the epoxy resin association area, for the utilization of xylogen, be mainly as reaction raw materials and filler.Xylogen is due to rigidity and huge structure, cause synthetic epoxide resin reactive very low, and due to the complicacy of lignin structure, the lignin structure of different biogenetic derivations and different areas biogenetic derivation of the same race is all different, causes synthetic epoxy resin unstable.Before the degraded of xylogen does not have industrialization, the xylogen epoxy resin synthetic as raw material is difficult to be applied.
If xylogen is as filler, application publication number is that the CN102585531A(application number is 201110417428.2) Chinese invention patent application disclose a kind ofly by the xylogen/epoxy resin composite material of precompressed and hot-press solidifying moulding, by ratio of quality and the number of copies, by the epoxy resin of 100 parts, the xylogen of 100~400 parts, the solidifying agent of 60~120 parts, the toughener of 0~40 part and the toughner of 0~20 part, made.Although the addition of the xylogen of this matrix material can reach more than 50%, it is just as a kind of filler, and added value is not high, and the relatively pure epoxy resin cured product of mechanical property of matrix material has reduced much simultaneously.
Application publication number is that the CN102753626A(application number is 201180008891.X) Chinese invention patent application a kind of resin combination is disclosed, for the resin combination that contains xylogen and solidifying agent, xylogen dissolves in organic solvent, and the xylogen that contains 10~90 quality %.In embodiment 1, in the xylogen of 100g, add bisphenol f type epoxy resin (solidifying agent) and the 1g1-cyano ethyl-2-phenylimidazole (curing catalyst) of 72g, and use mixing 5 minutes of the warming mill of 150 ℃.Use pulverizer to pulverize the mixing thing of gained, and the sieve that is 1mm through mesh, obtaining median size is 0.6 particle resin combination.The mechanical property of test formed body after curing molding, its flexural strength is 202MPa, and bending elastic modulus is 4.7GPa, and its flame retardant properties is HB grade (size of flame retardant resistance is divided into V-0, V-1, V-2, HB grade successively, and grade is successively decreased successively).Although it has good mechanical property, its flame retardant properties is poor.
Can improve again its added value (as flame retardant resistance) in the time of how using xylogen as filler and keep the mechanical property of matrix material is a developing direction of xylogen/polymer composites.
Summary of the invention
The invention provides a kind of fire-retardant epoxy resin/xylogen/organosilicon matrix material, under the prerequisite that guarantees its excellent mechanical performances, can improve its flame retardant resistance.
A kind of fire-retardant epoxy resin/xylogen/organosilicon matrix material is prepared from by following component according to the mass fraction:
Described epoxy group(ing) organic-silicon hybridization thing forms by silane compound and epoxyalkylsilane coupling agent hydrolysis condensation reaction.
In the present invention, the epoxy group(ing) organic-silicon hybridization thing obtained by hydrolysis condensation reaction, residual a large amount of silicon hydroxyl, when composite material solidification, the silicon hydroxyl easily with the xylogen surface reaction, epoxide group participates in curable epoxide, silane coupling agent more easily plays the effect of dispersion xylogen relatively.Epoxy group(ing) organic-silicon hybridization thing itself is a kind of Si-O-Si structure of branchedization, can form the charcoal layer that one deck is firm in combustion processes together with xylogen, play the further burning that hinders matrix material, improve flame retardant resistance, epoxy group(ing) organic-silicon hybridization thing and xylogen have played the effect of cooperative flame retardant.With respect to independent organosilicon or the epoxy resin of filled with lignin, flame retardant effect is better.Simultaneously, the introducing of epoxy group(ing) organic-silicon hybridization thing can improve the shock resistance of epoxy resin cured product.
Epoxy resin can adopt prior art, can adopt commercially available prod.As preferably, described epoxy resin is one or more (the comprising two kinds) in bisphenol A type epoxy resin, bisphenol f type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, novolac epoxy.Select above-mentioned epoxy resin as body material, can make the fire-retardant epoxy resin/xylogen of the present invention/organosilicon matrix material there is good mechanical property.
Xylogen can adopt prior art, can adopt commercially available prod.As preferably, described xylogen is sodium lignosulfonate, calcium lignin sulphonate, alkali lignin, xylogen sodium sulfate, xylogen calcium sulfate or enzymolysis xylogen.Select above-mentioned xylogen, not only can play the effect of filler, and, can also in combustion processes, together with epoxy group(ing) organic-silicon hybridization thing, can form the charcoal layer that one deck is firm, play the further burning that hinders matrix material and the effect that improves flame retardant resistance.
As preferably, described silane compound is one or more (the comprising two kinds) in methyltrimethoxy silane, ethyl trimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, Union carbide A-162, methyl triacetoxysilane, n-propyl Trimethoxy silane, n-propyl triethoxyl silane, n-octyl Trimethoxy silane, n-octyl triethoxyl silane, dodecyl Trimethoxy silane, METHYL TRICHLORO SILANE, tetramethoxy-silicane, tetraethoxysilane.
As preferably, described epoxyalkylsilane coupling agent is one or both in formula I structure, formula II structure;
Wherein, R is the straight chain that length that the carbonatoms straight chain that is 2~8 or at least one and carbon atom in Sauerstoffatom, sulphur atom and nitrogen-atoms are combined to form is 3~8, R 1for methyl, ethyl, n-propyl, sec.-propyl or butyl, R 2for methyl or ethyl, n is 2 or 3.In R in formula I and formula II, R can be identical or different, the R in formula I 1with R in formula II 1can be identical or different, the R in formula I 2with R in formula II 2can be identical or different.
Further preferably, described epoxyalkylsilane coupling agent is γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, 3-(2,3-epoxy the third oxygen) propyl-triethoxysilicane, 2-(3,4-epoxy cyclohexane base) ethyl trimethoxy silane, 2-(3,4-epoxy cyclohexane base) ethyl triethoxysilane, 8-(1, the 2-epoxy ethyl) octyl group Trimethoxy silane, 4-(1, the 2-epoxy ethyl) butyl trimethoxy silane, 3-(2,3-epoxy the third oxygen) one or more in propyl group methyl dimethoxysilane, 3-(2,3-epoxy the third oxygen) propyl group methyldiethoxysilane.
The residual a large amount of silicon hydroxyl of the epoxy group(ing) organic-silicon hybridization thing that above-mentioned silane compound and epoxyalkylsilane coupling agent generate by reaction, when composite material solidification, the silicon hydroxyl easily and the xylogen surface reaction, epoxide group participates in curable epoxide, xylogen is played to the effect disperseed better simultaneously.
Described solidifying agent is one or more (the comprising two kinds) in amine curing agent, acid anhydride type curing agent, resol, as preferably, described solidifying agent be diethylenetriamine, 4,4 '-one or more in diaminodiphenylmethane, amido amine, polymeric amide, polyetheramine, Dyhard RU 100, methyl hexahydrophthalic anhydride, itaconic anhydride, tung oil acid anhydride, resol.The consumption of described solidifying agent is 10~80 parts (quality).
Described curing catalyst is one or more (the comprising two kinds) in tertiary amine, quaternary amine, organic bases, Lewis acid, as preferably, described curing catalyst is glyoxal ethyline, Tetrabutyl amonium bromide, 2,4,6-tri-(dimethylamino methyl) phenol, boron trifluoride (BF 3) in one or more.
The present invention also provides the preparation method of a kind of fire-retardant epoxy resin/xylogen/organosilicon matrix material, and controllability is good, easy to implement.
The preparation method of a kind of fire-retardant epoxy resin/xylogen/organosilicon matrix material comprises the following steps:
1) silane compound, epoxyalkylsilane coupling agent, organic solvent, deionized water and catalyst mix is even, in 50~100 ℃ of reaction 2~10h, after removing organic solvent and water, obtain epoxy group(ing) organic-silicon hybridization thing;
2) first by epoxy resin, xylogen and epoxy group(ing) organic-silicon hybridization thing, mix, then add solidifying agent and curing catalyst, mix, after solidifying, obtain fire-retardant epoxy resin/xylogen/organosilicon matrix material.
In step 1), as preferably, the mass ratio of described silane compound, epoxyalkylsilane coupling agent, organic solvent, deionized water and catalyzer is 100:5~200:50~400:5~70:0.5~6, the epoxy group(ing) organic-silicon hybridization thing that adopts above-mentioned quality to prepare than raw material, combine with epoxy resin, xylogen, solidifying agent and curing catalyst, can better improve mechanical property and the flame retardant resistance of fire-retardant epoxy resin/xylogen/organosilicon matrix material.
Described organic solvent is ethers or alcohol organic solvent, is preferably one or more in tetrahydrofuran (THF), dioxane, ethanol.
Described catalyzer is carboxylate metal salt catalyzer, is preferably at least one in dibutyl tin laurate, dibutyl tin acetate and stannous octoate.
Step 2) in, as preferably, described solidifying comprises: first at 50~89 ℃, solidify 0~10 hour, then at 90~149 ℃, solidify 0~10 hour, then solidify 0~10 hour at 150~200 ℃.
As preferably, the preparation method of described fire-retardant epoxy resin/xylogen/organosilicon matrix material comprises the following steps:
(1) by tetraethoxysilane, methyltrimethoxy silane, 8-(1, the 2-epoxy ethyl) octyl group Trimethoxy silane, ethanol, deionized water and dibutyl tin acetate mix after at 78 ℃ of lower hydrolysis condensation reaction 5h, the underpressure distillation small-molecule substance, obtain epoxy group(ing) organic-silicon hybridization thing;
The mass ratio of described tetraethoxysilane, methyltrimethoxy silane, 8-(1,2-epoxy ethyl) octyl group Trimethoxy silane, ethanol, deionized water and dibutyl tin acetate is 70:30:200:400:70:6;
(2) epoxy group(ing) organic-silicon hybridization thing synthetic in glycidyl amine type epoxy resin, calcium lignin sulphonate and step (1) is mixed; Add again polyetheramine, mix, first solidify 4 hours under 70 ℃, then solidify 3 hours under 150 ℃, obtain fire-retardant epoxy resin/xylogen/organosilicon matrix material;
The mass ratio of described glycidyl amine type epoxy resin, calcium lignin sulphonate, epoxy group(ing) organic-silicon hybridization thing and polyetheramine is 100:100:100:70.
Fire-retardant epoxy resin/xylogen prepared by this concrete grammar/organosilicon matrix material has excellent flame retardant resistance and excellent mechanical property and higher second-order transition temperature.
With respect to prior art, the present invention has following advantage and beneficial effect:
The present invention fire-retardant epoxy resin/xylogen/the organosilicon matrix material is compound formulated by epoxy group(ing) organic-silicon hybridization thing, epoxy resin, xylogen and solidifying agent and curing catalyst, between each component, synergy is arranged, particularly between epoxy group(ing) organic-silicon hybridization thing, epoxy resin, xylogen, there is very strong synergy, its mechanical property excellence, good flame resistance.In the present invention, the epoxy group(ing) organic-silicon hybridization thing obtained by hydrolysis condensation reaction, residual a large amount of silicon hydroxyl, when composite material solidification, the silicon hydroxyl easily with the xylogen surface reaction, epoxide group participates in curable epoxide, silane coupling agent more easily plays the effect of dispersion xylogen relatively.Epoxy group(ing) organic-silicon hybridization thing itself is a kind of Si-O-Si structure of branchedization, can form the charcoal layer that one deck is firm in combustion processes together with xylogen, play the further burning that hinders matrix material, improve flame retardant resistance, epoxy group(ing) organic-silicon hybridization thing and xylogen have played the effect of cooperative flame retardant.With respect to independent organosilicon or the epoxy resin of filled with lignin, flame retardant effect is better.Simultaneously, the introducing of epoxy group(ing) organic-silicon hybridization thing can improve the shock resistance of epoxy resin cured product.
The preparation method of the fire-retardant epoxy resin/xylogen of the present invention/organosilicon matrix material, workable, controllability is good, easy to implement, is conducive to large-scale industrialization production.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
(1) by 70g tetraethoxysilane, 30g methyltrimethoxy silane, 200g8-(1, the 2-epoxy ethyl) octyl group Trimethoxy silane (Shanghai adds positive chemical industry company limited to be provided), 400g ethanol, 70g deionized water and 6g dibutyl tin acetate mix after at 78 ℃ of lower hydrolysis condensation reaction 5h, the small-molecule substances such as second alcohol and water are removed in underpressure distillation, obtain epoxy group(ing) organic-silicon hybridization thing.
(2) by synthetic epoxy group(ing) organic-silicon hybridization thing 100g in glycidyl amine type epoxy resin (AG80, Hubei precious posivtive spike novel material company limited provides) 100g, calcium lignin sulphonate 100g and step (1), utilize ball mill to mix; Add again polyetheramine (D230, Aladdin provides) 70g, be uniformly mixed, first solidify 4 hours under 70 ℃, then solidify 3 hours under 150 ℃, obtain fire-retardant epoxy resin/xylogen/organosilicon matrix material.
After testing, the flame retardant properties of this fire-retardant epoxy resin/xylogen/organosilicon matrix material reaches UL-94V0, and resistance to impact shock is 65kJm -2(resistance to impact shock is measured with balance weight impact testing machine, and sample is rectangular parallelepiped, is of a size of 60 * 6 * 4.5mm 3, lower with), second-order transition temperature (Tg) be 125 ℃ (after sample solidifies, grinding powder, produce the test of MET type differential scanning calorimeter with Mettler Toledo Inc., N2 atmosphere, temperature rise rate is 20 ℃/min, lower with).
Comparative Examples:
When not adding calcium lignin sulphonate, epoxy group(ing) organic-silicon hybridization thing, by glycidyl amine type epoxy resin (AG80, Hubei precious posivtive spike novel material company limited provides) 100g and polyetheramine (D230, Aladdin provides) 70g, be uniformly mixed, first under 70 ℃, solidify 4 hours, then solidify 3 hours under 150 ℃, obtain epoxide resin material.The flame retardant properties of this epoxide resin material reaches UL-94 without rank, and resistance to impact shock is 60kJm -2, Tg is 115 ℃.
When not adding calcium lignin sulphonate, by glycidyl amine type epoxy resin (AG80, Hubei precious posivtive spike novel material company limited provides) synthetic epoxy group(ing) organic-silicon hybridization thing 100g and the polyetheramine (D230 of 100g, embodiment 1, Aladdin provides) 70g, be uniformly mixed, first under 70 ℃, solidify 4 hours, then solidify 3 hours under 150 ℃, obtain epoxy resin/organosilicon matrix material.The flame retardant properties of this epoxy resin/organosilicon matrix material reaches UL-94 without rank, and resistance to impact shock is 65kJm -2, Tg is 120 ℃.
When not adding epoxy group(ing) organic-silicon hybridization thing, by glycidyl amine type epoxy resin (AG80, Hubei precious posivtive spike novel material company limited provides) 100g, calcium lignin sulphonate 100g and polyetheramine (D230, Aladdin provides) 70g, be uniformly mixed, first under 70 ℃, solidify 4 hours, then solidify 3 hours under 150 ℃, obtain epoxy resin/lignin composite material.The flame retardant properties of this epoxy resin/lignin composite material reaches UL-94V1, and resistance to impact shock is 45kJm -2, Tg is 117 ℃.
Embodiment 1 is more known with Comparative Examples, adopt the flame retardant properties of epoxy resin/xylogen of the present invention/organosilicon matrix material to be greatly improved, shock resistance and second-order transition temperature are maintained.
Embodiment 2
(1) by 100g methyl triacetoxysilane, 5g4-(1, the 2-epoxy ethyl) butyl trimethoxy silane (Shanghai adds positive chemical industry company limited to be provided), 100g tetrahydrofuran (THF), 10g deionized water and 0.5g dibutyl tin laurate mix after at 65 ℃ of lower hydrolysis condensation reaction 9h, the small-molecule substances such as tetrahydrofuran (THF) and water are removed in underpressure distillation, obtain epoxy group(ing) organic-silicon hybridization thing.
(2) by synthetic epoxy group(ing) organic-silicon hybridization thing 1g in bisphenol A type epoxy resin (E-51, Shenzhen Jitian's chemical industry company limited provides) 100g, sodium lignosulfonate 5g and step (1), utilize ball mill to mix; Add again 4,4 '-diaminodiphenylmethane 25g, be uniformly mixed, first under 90 ℃, solidify 2 hours, then under 150 ℃, solidify 2 hours, finally under 180 ℃, solidify 2 hours, obtain fire-retardant epoxy resin/xylogen/organosilicon matrix material.
The flame retardant properties of this material reaches UL-94V1, and resistance to impact shock is 18kJm -2, Tg is 165 ℃.
Embodiment 3
(1) by 50g METHYL TRICHLORO SILANE, 50g n-octyl Trimethoxy silane, 30g3-(2,3-epoxy the third oxygen) propyl group methyl dimethoxysilane, 50g tetrahydrofuran (THF), 5g deionized water and 2g dibutyl tin acetate mix after 50 ℃ of lower hydrolysis condensation reactions 10 hours, the small-molecule substances such as tetrahydrofuran (THF) and water are removed in underpressure distillation, obtain epoxy group(ing) organic-silicon hybridization thing.
(2) by epoxy group(ing) organic-silicon hybridization thing 80g synthetic in glycidyl ester type epoxy resin (o-phthalic acid diglycidyl ester) 100g, alkali lignin 80g and step (1), utilize ball mill to mix; Add again diethylenetriamine 20g, tung oil acid anhydride 5g and Tetrabutyl amonium bromide 2g, be uniformly mixed, first solidify 10 hours under 50 ℃, then solidify 1 hour under 90 ℃, solidify 1 hour under 160 ℃ again, obtain fire-retardant epoxy resin/xylogen/organosilicon matrix material.
The flame retardant properties of this material reaches UL-94V0, and resistance to impact shock is 20kJm -2, Tg is 170 ℃.
Embodiment 4
(1) by 100g Union carbide A-162,10g3-(2,3-epoxy the third oxygen) propyl group methyldiethoxysilane, 70g dioxane, 20g deionized water and 1g dibutyl tin acetate mix after 100 ℃ of lower hydrolysis condensation reactions 2 hours, the small-molecule substances such as tetrahydrofuran (THF) and water are removed in underpressure distillation, obtain epoxy group(ing) organic-silicon hybridization thing.
(2) by bisphenol f type epoxy resin (D.E.R. tM354, DOW Chemical provides) synthetic epoxy group(ing) organic-silicon hybridization thing 25g in 100g, xylogen sodium sulfate 30g and step (1), utilize ball mill to mix; Add again itaconic anhydride 55g and glyoxal ethyline 5g, be uniformly mixed, solidify under 7 hours, 190 ℃ and solidify 3 hours under 120 ℃, obtain fire-retardant epoxy resin/xylogen/organosilicon matrix material.
The flame retardant properties of this material reaches UL-94V1, and resistance to impact shock is 30kJm -2, Tg is 145 ℃.
Embodiment 5
(1) by 100g phenyltrimethoxysila,e, 100g2-(3,4-epoxy cyclohexane base) ethyl trimethoxy silane, 200g dioxane, 50g deionized water and 5g stannous octoate mix after at 80 ℃ of lower hydrolysis condensation reaction 4h, the small-molecule substances such as dioxane and water are removed in underpressure distillation, obtain epoxy group(ing) organic-silicon hybridization thing.
(2) by synthetic epoxy group(ing) organic-silicon hybridization thing 1g in novolac epoxy (NPPN-631, South Asia plastics industry limited-liability company provides) 100g, xylogen calcium sulfate 20g and step (1), utilize ball mill to mix; Add again polymeric amide (grinding scientific and technological Industrial Co., Ltd in Xuzhou provides) 80g and 2,4,6-tri-(dimethylamino methyl) phenol 6g, be uniformly mixed, first under 80 ℃, solidify 6 hours, then solidify 5 hours under 130 ℃, then solidify 5 hours under 170 ℃, obtain fire-retardant epoxy resin/xylogen/organosilicon matrix material.
The flame retardant properties of this material reaches UL-94V1, and resistance to impact shock is 50kJm -2, Tg is 100 ℃.
Embodiment 6
(1) by 100g ethyl trimethoxy silane, 90g γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane (KH-560), 60g2-(3,4-epoxy cyclohexane base) ethyl triethoxysilane, 200g tetrahydrofuran (THF), 100g ethanol, 15g deionized water and 1.2g dibutyl tin laurate mix after at 65 ℃ of lower hydrolysis condensation reaction 7h, the small-molecule substances such as tetrahydrofuran (THF) and water are removed in underpressure distillation, obtain epoxy group(ing) organic-silicon hybridization thing.
(2) by bisphenol A type epoxy resin (CYD-014U, Yueyang petrochemical industry company limited of Ba Ling Huaxing provides) 70g, bisphenol f type epoxy resin (EPICLON830LVP, large Japanese ink company provides) synthetic epoxy group(ing) organic-silicon hybridization thing 10g in 30g, enzymolysis xylogen 45g and step (1), utilize ball mill to mix; Add again resol 10g and glyoxal ethyline 4g, be uniformly mixed, first solidify 10 hours under 140 ℃, then solidify 1 hour under 200 ℃, obtain fire-retardant epoxy resin/xylogen/organosilicon matrix material.
The flame retardant properties of this material reaches UL-94V1, and resistance to impact shock is 36kJm -2, Tg is 120 ℃.
Embodiment 7
(1) by 100g dodecyl Trimethoxy silane, 60g3-(2,3-epoxy the third oxygen) propyl-triethoxysilicane, 150g tetrahydrofuran (THF), 35g deionized water and 3g dibutyl tin laurate mix after at 60 ℃ of lower hydrolysis condensation reaction 8h, the small-molecule substances such as tetrahydrofuran (THF) and water are removed in underpressure distillation, obtain epoxy group(ing) organic-silicon hybridization thing.
(2) by bisphenol A type epoxy resin (E-54, Lanxing Chemical New Material Co., Ltd. provides) 80g, bisphenol A type epoxy resin (E-20, Lanxing Chemical New Material Co., Ltd. provides) synthetic epoxy group(ing) organic-silicon hybridization thing 60g in 20g, calcium lignin sulphonate 60g and step (1), utilize ball mill to mix; Add again Dyhard RU 100 50g and boron trifluoride (BF 3) 1g, be uniformly mixed, first under 60 ℃, solidify 8 hours, then under 100 ℃, solidify 4 hours, finally under 150 ℃, solidify 10 hours, obtain fire-retardant epoxy resin/xylogen/organosilicon matrix material.
The flame retardant properties of this material reaches UL-94V0, and resistance to impact shock is 28kJm -2, Tg is 155 ℃.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.

Claims (10)

1. fire-retardant epoxy resin/xylogen/organosilicon matrix material, is characterized in that, by following component according to the mass fraction, is prepared from:
Described epoxy group(ing) organic-silicon hybridization thing forms by silane compound and epoxyalkylsilane coupling agent hydrolysis condensation reaction.
2. fire-retardant epoxy resin/xylogen according to claim 1/organosilicon matrix material, it is characterized in that, described epoxy resin is one or more in bisphenol A type epoxy resin, bisphenol f type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, novolac epoxy.
3. fire-retardant epoxy resin/xylogen according to claim 1/organosilicon matrix material, it is characterized in that, described xylogen is sodium lignosulfonate, calcium lignin sulphonate, alkali lignin, xylogen sodium sulfate, xylogen calcium sulfate or enzymolysis xylogen.
4. fire-retardant epoxy resin/xylogen according to claim 1/organosilicon matrix material, it is characterized in that, described silane compound is methyltrimethoxy silane, ethyl trimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, Union carbide A-162, methyl triacetoxysilane, the n-propyl Trimethoxy silane, the n-propyl triethoxyl silane, the n-octyl Trimethoxy silane, the n-octyl triethoxyl silane, the dodecyl Trimethoxy silane, METHYL TRICHLORO SILANE, tetramethoxy-silicane, one or more in tetraethoxysilane.
5. fire-retardant epoxy resin/xylogen according to claim 1/organosilicon matrix material, is characterized in that, described epoxyalkylsilane coupling agent is one or both in formula I structure, formula II structure;
Wherein, R is the straight chain that length that the carbonatoms straight chain that is 2~8 or at least one and carbon atom in Sauerstoffatom, sulphur atom and nitrogen-atoms are combined to form is 3~8, R 1for methyl, ethyl, n-propyl, sec.-propyl or butyl, R 2for methyl or ethyl, n is 2 or 3.
6. fire-retardant epoxy resin/xylogen according to claim 5/organosilicon matrix material, it is characterized in that, described epoxyalkylsilane coupling agent is γ-(2, 3-epoxy the third oxygen) propyl trimethoxy silicane, 3-(2, 3-epoxy the third oxygen) propyl-triethoxysilicane, 2-(3, 4-epoxy cyclohexane base) ethyl trimethoxy silane, 2-(3, 4-epoxy cyclohexane base) ethyl triethoxysilane, 8-(1, the 2-epoxy ethyl) octyl group Trimethoxy silane, 4-(1, the 2-epoxy ethyl) butyl trimethoxy silane, 3-(2, 3-epoxy the third oxygen) propyl group methyl dimethoxysilane, 3-(2, 3-epoxy the third oxygen) one or more in the propyl group methyldiethoxysilane.
7. fire-retardant epoxy resin/xylogen according to claim 1/organosilicon matrix material, it is characterized in that, described solidifying agent be diethylenetriamine, 4,4 '-one or more in diaminodiphenylmethane, amido amine, polymeric amide, polyetheramine, Dyhard RU 100, methyl hexahydrophthalic anhydride, itaconic anhydride, tung oil acid anhydride, resol.
8. fire-retardant epoxy resin/xylogen according to claim 1/organosilicon matrix material, it is characterized in that, described curing catalyst is glyoxal ethyline, Tetrabutyl amonium bromide, 2,4, one or more in 6-tri-(dimethylamino methyl) phenol, boron trifluoride.
9. according to the preparation method of the described fire-retardant epoxy resin/xylogen of claim 1~8 any one/organosilicon matrix material, it is characterized in that, comprise the following steps:
1) silane compound, epoxyalkylsilane coupling agent, organic solvent, deionized water and catalyst mix is even, in 50~100 ℃ of reaction 2~10h, after removing organic solvent and water, obtain epoxy group(ing) organic-silicon hybridization thing;
2) first by epoxy resin, xylogen and epoxy group(ing) organic-silicon hybridization thing, mix, then add solidifying agent and curing catalyst, mix, after solidifying, obtain fire-retardant epoxy resin/xylogen/organosilicon matrix material.
10. the preparation method of fire-retardant epoxy resin/xylogen according to claim 9/organosilicon matrix material, it is characterized in that, in step 1), the mass ratio of described silane compound, epoxyalkylsilane coupling agent, organic solvent, deionized water and catalyzer is 100:5~200:50~400:5~70:0.5~6.
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CN106243141A (en) * 2016-08-01 2016-12-21 常州聚博节能科技有限公司 Inorganic hybridization methylolated lignin and preparation method thereof
CN108003566A (en) * 2017-12-20 2018-05-08 无锡盛雅生物科技有限公司佛山分公司 A kind of shockproof mesa material of intermetallic composite coating and preparation method thereof
CN109096700A (en) * 2018-08-01 2018-12-28 张国军 A kind of ground moisture retardant composition epoxy resin
CN109880293A (en) * 2019-01-30 2019-06-14 中国人民解放军国防科技大学 It is a kind of epoxy resin toughened and preparation method thereof
CN112898586A (en) * 2021-01-22 2021-06-04 南京大学 Preparation method of epoxy group-containing hyperbranched organic silicon resin and compound thereof

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CN102585531A (en) * 2011-12-14 2012-07-18 东北林业大学 Lignin-epoxy resin composite material and preparation method thereof

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104493932A (en) * 2014-12-01 2015-04-08 公安部四川消防研究所 Water-based flame retardant liquid for historic building and preparation method of water-based flame retardant
CN106243141A (en) * 2016-08-01 2016-12-21 常州聚博节能科技有限公司 Inorganic hybridization methylolated lignin and preparation method thereof
CN108003566A (en) * 2017-12-20 2018-05-08 无锡盛雅生物科技有限公司佛山分公司 A kind of shockproof mesa material of intermetallic composite coating and preparation method thereof
CN109096700A (en) * 2018-08-01 2018-12-28 张国军 A kind of ground moisture retardant composition epoxy resin
CN109880293A (en) * 2019-01-30 2019-06-14 中国人民解放军国防科技大学 It is a kind of epoxy resin toughened and preparation method thereof
CN112898586A (en) * 2021-01-22 2021-06-04 南京大学 Preparation method of epoxy group-containing hyperbranched organic silicon resin and compound thereof

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