CN103525346B - Boron-modified phenolic resin adhesive - Google Patents
Boron-modified phenolic resin adhesive Download PDFInfo
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- CN103525346B CN103525346B CN201310377365.1A CN201310377365A CN103525346B CN 103525346 B CN103525346 B CN 103525346B CN 201310377365 A CN201310377365 A CN 201310377365A CN 103525346 B CN103525346 B CN 103525346B
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- modified phenolic
- phenolic resin
- polyborosiloxane
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- boron
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title abstract description 9
- 239000000853 adhesive Substances 0.000 title abstract description 7
- 230000001070 adhesive effect Effects 0.000 title abstract description 7
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 20
- 239000005011 phenolic resin Substances 0.000 claims abstract description 20
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 41
- -1 boron modified phenolic resin Chemical class 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052796 boron Inorganic materials 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 15
- 239000004327 boric acid Substances 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000004513 sizing Methods 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 125000005375 organosiloxane group Chemical group 0.000 claims description 11
- 235000013824 polyphenols Nutrition 0.000 claims description 9
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 6
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229920000052 poly(p-xylylene) Polymers 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229920003987 resole Polymers 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 4
- 229960001755 resorcinol Drugs 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 2
- 229960001553 phloroglucinol Drugs 0.000 claims description 2
- 229940079877 pyrogallol Drugs 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 125000000532 dioxanyl group Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- 239000007789 gas Substances 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- 239000003607 modifier Substances 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical group COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Silicon Polymers (AREA)
Abstract
The invention relates to a boron-modified phenolic resin adhesive which is characterized in that a preparation method of the boron-modified phenolic resin adhesive comprises the following steps: I, synthesizing polyborosiloxane (PBSH); II, synthesizing modified phenolic resin; and III, preparing the boron-modified phenolic resin adhesive. The method for preparing the polyborosiloxane in the boron-modified phenolic resin adhesive is relatively mild in condition, simple to operate, free from generation of harmful gases and green and environment-friendly. The obtained polyborosiloxane is excellent in high temperature resistance, and contains a plenty of terminal hydroxyls. The polyborosiloxane used as a modifier can improve the high temperature resistance and the bonding strength of the phenolic resin at the same time, thereby providing a feasible method for preparing the high temperature resistant phenolic resin adhesive.
Description
Technical field
The invention belongs to chemical field, relate in particular to a kind of polyborosiloxane and synthetic sizing agent of modified phenolic resins of utilizing.
Background technology
Resol price is very low, raw material has easily been bought, production technique and production unit simple, become one of indispensable material of industrial sector, apply very extensive.Pure phenolic aldehyde resin thermal stability and high thermal resistance are not high enough, and people have carried out large quantity research to its modification, to improve its thermotolerance and cohesive strength.
Polyborosiloxane (PBS) has excellent resistance toheat.There are research and utilization boric acid and organosilicon preformed polymer to prepare polyborosiloxane, and use it for the modification of resol, resin carbon residue rate after modification significantly improves, (the Zhang Bin etc. but the cohesive force of the phenolic resin adhesive after modification is not significantly improved, polymer material science and engineering, 2008,152).There is research in polyborosiloxane, to introduce Resorcinol structure, obtain polyborosiloxane PBSH, the following technological line of main employing is prepared PBSH at present: in nitrogen atmosphere, first by two halosilanes and boric acid, carry out bulk reaction, add afterwards Resorcinol solution to continue reaction, obtain PBSH(expense ease big, coatings industry .19913,8).In above-mentioned route, there is following problem: wherein adopt halosilanes and acid reaction, generate the HCl gas that has pungent odour, there is very high corrodibility.
Summary of the invention
The present invention has designed a kind of boron modified phenolic resin sizing agent, and it is high temperature resistant altogether that its object is to provide, and the sizing agent of high bond strength, improves the preparation method of polyborosiloxane (PBSH) meanwhile, overcomes the problems of the prior art.
To achieve these goals, the present invention has adopted following scheme:
A boron modified phenolic resin sizing agent, is characterized in that comprising following steps:
Step 1: synthetic polyborosiloxane (PBSH);
Step 2: synthesis modification resol;
Step 3: prepare boron modified phenolic resin sizing agent.
Described step 1 is that organo-siloxane and boric acid are joined in organic solvent, under the condition existing, in nitrogen atmosphere, is progressively warmed up to 200 ℃, reaction 1-5h in lower 3 hours from 90 ℃ at catalyzer; Then add polyphenol, reaction 4-10h, after water pump Depressor response 1.5～3h, obtains polyborosiloxane (PBSH);
Described step 2 is to get an acidic catalyst of the methoxyl group parylene monomer of 20 weight parts, the Resorcinol of 20 weight parts and 1.5 weight parts, under the condition of 125 ℃, react 1-4h, after cooling down, the formaldehyde that adds the basic catalyst of 1.5 weight parts, the organic solvent of 12 weight parts and 18 weight parts, dehydration reaction under the vacuum of 0.6KPa obtains modified phenolic resins after transparent;
Described step 3 is to get the modified phenolic resins that the polyborosiloxane that makes in step 1 and step 2 make to mix by the mass ratio of 1-6:10, obtains boron modified phenolic resin tackiness agent.
Organo-siloxane described in step 1: boric acid: the mol ratio of polyphenol is 1:1～2:0.25～1, catalyst levels is 1 of monomer total mass～2 ‰.
Described in step 1, organo-siloxane is the mixture that phenyltrimethoxysila,e and methyltrimethoxy silane are made according to weight fraction 1:2.
Described in step 1, solvent is diethylene glycol dimethyl ether or dioxane.
Described in step 1, catalyzer is any one in tin protochloride, titanium tetrachloride, Indian red.
Polyphenol described in step 1 is a kind of or several mixing in pyrocatechol, Resorcinol, Resorcinol, Phloroglucinol, pyrogallol.
The tosic acid that described in step 2, an acidic catalyst is 25wt%, the ammoniacal liquor that described basic catalyst is 20wt%, described organic solvent is vinylbenzene.
Described in step 3, the mass ratio of polyborosiloxane and modified phenolic resins is 2-5:10.
This boron modified phenolic resin sizing agent has following beneficial effect: 1, the present invention is by organo-siloxane and boric acid, polyphenol polycondensation, the synthetic polyborosiloxane that contains a large amount of terminal hydroxy group and have excellent heat resistance; After mixing with resol, can improve its thermotolerance and bonding strength.
2, the present invention prepares polyborosiloxane method mild condition, simple to operate, without harmful gas generation, environmental protection, and gained polyborosiloxane resistance to elevated temperatures is excellent.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described:
Embodiment 1
Step 1: mixture and boric acid that phenyltrimethoxysila,e and methyltrimethoxy silane are made according to weight fraction 1:2 join in diethylene glycol dimethyl ether, under the condition existing at tin protochloride, in lower 3 hours of nitrogen atmosphere, be progressively warmed up to 200 ℃ from 90 ℃, continue reaction 5h; Then add Resorcinol, reaction 6h, after water pump Depressor response 2h, obtains polyborosiloxane (PBSH); Organo-siloxane: boric acid: the mol ratio of Resorcinol is 1:1:1, catalyst levels is 1 ‰ of monomer total mass;
Step 2: the tosic acid of getting the 25wt% of the methoxyl group parylene monomer of 20 weight parts, the Resorcinol of 20 weight parts and 1.5 weight parts, under the condition of 125 ℃, react 2h, after cooling down, the formaldehyde that adds the ammoniacal liquor of the 20wt% of 1.5 weight parts, the vinylbenzene of 12 weight parts and 18 weight parts, dehydration reaction under the vacuum of 0.6KPa obtains modified phenolic resins after transparent;
Step 3: get the modified phenolic resins that the polyborosiloxane that makes in step 1 and step 2 make and mix by the mass ratio of 2:10, obtain boron modified phenolic resin tackiness agent.
Embodiment 2
Step 1: mixture and boric acid that phenyltrimethoxysila,e and methyltrimethoxy silane are made according to weight fraction 1:2 join in dioxane, under the condition existing at tin protochloride, in lower 3 hours of nitrogen atmosphere, be progressively warmed up to 200 ℃ from 90 ℃, continue reaction 5h; Then add Resorcinol, reaction 6h, after water pump Depressor response 2h, obtains polyborosiloxane (PBSH); Organo-siloxane: boric acid: the mol ratio of Resorcinol is 1:1:1, catalyst levels is 1 ‰ of monomer total mass;
Step 2: the tosic acid of getting the 25wt% of the methoxyl group parylene monomer of 20 weight parts, the Resorcinol of 20 weight parts and 1.5 weight parts, under the condition of 125 ℃, react 2h, after cooling down, the formaldehyde that adds the ammoniacal liquor of the 20wt% of 1.5 weight parts, the vinylbenzene of 12 weight parts and 18 weight parts, dehydration reaction under the vacuum of 0.6KPa obtains modified phenolic resins after transparent;
Step 3: get the modified phenolic resins that the polyborosiloxane that makes in step 1 and step 2 make and mix by the mass ratio of 3:10, obtain boron modified phenolic resin tackiness agent.
Embodiment 3
Step 1: mixture and boric acid that phenyltrimethoxysila,e and methyltrimethoxy silane are made according to weight fraction 1:2 join in dioxane, under the condition existing at titanium tetrachloride, in lower 3 hours of nitrogen atmosphere, be progressively warmed up to 200 ℃ from 90 ℃, continue reaction 5h; Then add Resorcinol, reaction 6h, after water pump Depressor response 2h, obtains polyborosiloxane (PBSH); Organo-siloxane: boric acid: the mol ratio of Resorcinol is 1:1:1, catalyst levels is 1 ‰ of monomer total mass;
Step 2: the tosic acid of getting the 25wt% of the methoxyl group parylene monomer of 20 weight parts, the Resorcinol of 20 weight parts and 1.5 weight parts, under the condition of 125 ℃, react 2h, after cooling down, the formaldehyde that adds the ammoniacal liquor of the 20wt% of 1.5 weight parts, the vinylbenzene of 12 weight parts and 18 weight parts, dehydration reaction under the vacuum of 0.6KPa obtains modified phenolic resins after transparent;
Step 3: get the modified phenolic resins that the polyborosiloxane that makes in step 1 and step 2 make and mix by the mass ratio of 4:10, obtain boron modified phenolic resin tackiness agent.
Embodiment 4
Step 1: mixture and boric acid that phenyltrimethoxysila,e and methyltrimethoxy silane are made according to weight fraction 1:2 join in diethylene glycol dimethyl ether, under the condition existing at Indian red, in lower 3 hours of nitrogen atmosphere, be progressively warmed up to 200 ℃ from 90 ℃, continue reaction 5h; Then add Resorcinol, reaction 6h, after water pump Depressor response 2h, obtains polyborosiloxane (PBSH); Organo-siloxane: boric acid: the mol ratio of Resorcinol is 1:1:1, catalyst levels is 1 ‰ of monomer total mass;
Step 2: the tosic acid of getting the 25wt% of the methoxyl group parylene monomer of 20 weight parts, the Resorcinol of 20 weight parts and 1.5 weight parts, under the condition of 125 ℃, react 2h, after cooling down, the formaldehyde that adds the ammoniacal liquor of the 20wt% of 1.5 weight parts, the vinylbenzene of 12 weight parts and 18 weight parts, dehydration reaction under the vacuum of 0.6KPa obtains modified phenolic resins after transparent;
Step 3: get the modified phenolic resins that the polyborosiloxane that makes in step 1 and step 2 make and mix by the mass ratio of 5:10, obtain boron modified phenolic resin tackiness agent.
Polyphenol in above-described embodiment 1-4 has all been selected Resorcinol, in the essentially identical situation of all the other conditions, only change the reaction ratio of polyborosiloxane and modified phenolic resins, then to the product obtaining in embodiment through gluing, solidify, measure its cohesive strength.Experimental result shows, the cohesive strength of the sizing agent obtaining when polyborosiloxane and modified phenolic resins mix by the mass ratio of 4:10 is maximum.
The present invention has been carried out to exemplary description above in conjunction with the embodiments; obvious realization of the present invention is not subject to the restrictions described above; as long as the various improvement that adopted method design of the present invention and technical scheme to carry out; or without improving, design of the present invention and technical scheme are directly applied to other occasion, all in protection scope of the present invention.
Claims (4)
1. a boron modified phenolic resin sizing agent, is characterized in that: by following steps, make; Step 1: synthetic polyborosiloxane (PBSH); Step 2: synthesis modification resol; Step 3: prepare boron modified phenolic resin sizing agent; Described step 1 is that organo-siloxane and boric acid are joined in organic solvent, under the condition existing, in nitrogen atmosphere, is progressively warmed up to 200 ℃, reaction 1-5h in lower 3 hours from 90 ℃ at catalyzer; Then add polyphenol, reaction 4-10h, after water pump Depressor response 1.5～3h, obtains polyborosiloxane (PBSH); Organo-siloxane described in step 1: boric acid: the mol ratio of polyphenol is 1:1～2:0.25～1, catalyst levels is 1 of monomer total mass～2 ‰; Described in step 1, organo-siloxane is the mixture that phenyltrimethoxysila,e and methyltrimethoxy silane are made according to weight fraction 1:2; Described in step 1, solvent is dioxane; Described in step 1, catalyzer is any one in tin protochloride, titanium tetrachloride, Indian red; Described step 2 is to get an acidic catalyst of the methoxyl group parylene monomer of 20 weight parts, the Resorcinol of 20 weight parts and 1.5 weight parts, under the condition of 125 ℃, react 1-4h, after cooling down, the formaldehyde that adds the basic catalyst of 1.5 weight parts, the organic solvent of 12 weight parts and 18 weight parts, dehydration reaction under the vacuum of 0.6KPa obtains modified phenolic resins after transparent; Described step 3 is to get the modified phenolic resins that the polyborosiloxane that makes in step 1 and step 2 make to mix by the mass ratio of 1-6:10, obtains boron modified phenolic resin tackiness agent.
2. boron modified phenolic resin sizing agent according to claim 1, is characterized in that: the polyphenol described in step 1 is a kind of or several mixing in pyrocatechol, Resorcinol, Resorcinol, Phloroglucinol, pyrogallol.
3. boron modified phenolic resin sizing agent according to claim 1, is characterized in that: the tosic acid that described in step 2, an acidic catalyst is 25wt%, and the ammoniacal liquor that described basic catalyst is 20wt%, described organic solvent is vinylbenzene.
4. boron modified phenolic resin sizing agent according to claim 1, is characterized in that: described in step 3, the mass ratio of polyborosiloxane and modified phenolic resins is 2-5:10.
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| CN201510022692.4A CN104650785B (en) | 2013-08-27 | 2013-08-27 | A kind of boron modified phenolic resin sizing agent |
| CN201310377365.1A CN103525346B (en) | 2013-08-27 | 2013-08-27 | Boron-modified phenolic resin adhesive |
| CN201510022691.XA CN104650784B (en) | 2013-08-27 | 2013-08-27 | A kind of boron modified phenolic resin sizing agent |
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| CN104448176B (en) * | 2014-12-22 | 2016-08-17 | 沙县宏盛塑料有限公司 | The preparation method of a kind of phenol-formaldehyde resin modified and the phenol-formaldehyde resin modified prepared by the method |
| CN105837770B (en) * | 2016-05-09 | 2018-01-02 | 盐城仁创砂业科技有限公司 | A kind of Modification Phenol-formaldehyde Resin for Casting and preparation method thereof |
| CN109734920A (en) * | 2018-12-17 | 2019-05-10 | 烟台德邦科技有限公司 | Preparation method of boron-containing adhesive |
| CN111793455A (en) * | 2020-07-28 | 2020-10-20 | 安徽大松树脂有限公司 | Preparation method of heat-resistant, oil-resistant and flexibility-resistant wood adhesive |
| CN114163593A (en) * | 2022-02-15 | 2022-03-11 | 北京玻钢院复合材料有限公司 | Polyether modified phenolic resin for heavy-load grinding wheel and preparation method thereof |
| CN114835903B (en) * | 2022-04-28 | 2023-03-14 | 北京理工大学 | Boron-containing silsesquioxane and preparation method thereof, modified phenolic resin and preparation method and application thereof |
| CN115322699A (en) * | 2022-07-26 | 2022-11-11 | 成都航天明江科技实业有限公司 | Pressure-sensitive adhesive tape with instant high temperature resistance of 550 DEG C |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN104650784B (en) | 2015-09-23 |
| CN104650784A (en) | 2015-05-27 |
| CN104650785B (en) | 2015-09-23 |
| CN104650785A (en) | 2015-05-27 |
| CN103525346A (en) | 2014-01-22 |
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