A kind of boron modified phenolic resin sizing agent
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.