CN103936952B - A kind of preparation method of modified rubber tackiness agent resorcinol formaldehyde resin - Google Patents
A kind of preparation method of modified rubber tackiness agent resorcinol formaldehyde resin Download PDFInfo
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- CN103936952B CN103936952B CN201410188527.1A CN201410188527A CN103936952B CN 103936952 B CN103936952 B CN 103936952B CN 201410188527 A CN201410188527 A CN 201410188527A CN 103936952 B CN103936952 B CN 103936952B
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Abstract
The invention discloses a kind of preparation method of modified rubber tackiness agent resorcinol formaldehyde resin, it comprises the steps: a) to drop in organic solvent alkylphenol, paraformaldehyde, stirs at 40 ~ 70 DEG C; B) 1 ~ 4 hour is incubated after dripping alkali lye; C) by step b) product heats to 80 ~ 100 DEG C that obtain, be incubated and be cooled to less than 90 DEG C after 2 ~ 4 hours; D) in step c) product that obtains adds acidity regulator, and add Resorcinol after stirring and be warming up to 100 ~ 150 DEG C of back flow reaction 2 ~ 5 hours; E) by step b) product that obtains removing organic solvent, start when product softening temperature is 99 ~ 109 DEG C to carry out granulation, obtain granular resorcinol formaldehyde resin.Advantage of the present invention substitutes formalin with paraformaldehyde, feeds intake simple, dangerous reduction.
Description
Technical field
The present invention relates to a kind of preparation method of modified rubber tackiness agent resorcinol formaldehyde resin, belong to chemical industry technical field of adhesive.
Background technology
Resorcinol formaldehyde resin can be used as the methylene receptor tackiness agent in m-first-lean type system, and with alternative Resorcinol monomer, (Resorcinol monomer or Resorcinol mixture in use dust are too large, not environmentally).Resorcinol formaldehyde resin can produce adhesive effect by reacting with methylene radical donor, for the bonding of rubber and framework material (as the metallic framework in tire and cord), also can be used as the additive of resol simultaneously, to reduce process period, reduce processing temperature.The range of application of resorcinol formaldehyde resin comprises: produce sand paper, emery wheel, clutch equipment, plywood adhesive etc., common production for Resorcinol and formalin for raw material, Resorcinol, inorganic salt and organic solvent is added in water solvent, then under acid catalyst effect, formalin is dripped, synthesized by liquid-liquid-liquid heterogeneous reaction, then water layer is removed, use organic solvent extraction again, washing, finally distillation removing organic solvent is to obtain resorcinol formaldehyde resin, and such production process is complicated; Product water content is high; Easily dissociate in use procedure Resorcinol, inadequate environmental protection; Volatility is high, and easily absorb water caking.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of modified rubber tackiness agent resorcinol formaldehyde resin to solve the problems referred to above existed in the manufacture of resorcinol formaldehyde resin in prior art.
A preparation method for modified rubber tackiness agent resorcinol formaldehyde resin, it comprises the steps:
A) will drop in organic solvent alkylphenol, paraformaldehyde, stir at 40 ~ 70 DEG C;
B) be incubated 1 ~ 4 hour after dripping alkali lye, the dripping quantity of alkali lye is 2 ~ 5% of paraformaldehyde mole number;
C) by step b) product heats to 80 ~ 100 DEG C that obtain, be incubated and be cooled to less than 90 DEG C after 2 ~ 4 hours;
D) in step c) add acidity regulator neutralization in the product that obtains, the dosage of described acidity regulator is 50% of alkali lye mole number, adds Resorcinol and be warming up to 100 ~ 150 DEG C of back flow reaction 2 ~ 5 hours after stirring;
E) by step b) product that obtains removing organic solvent, start when product softening temperature is 99 ~ 109 DEG C to carry out granulation, obtain granular resorcinol formaldehyde resin.
Preferably, the described mol ratio to alkylphenol and paraformaldehyde is 1:1 ~ 1:2.
Preferably, the mol ratio of described paraformaldehyde and Resorcinol is 1.5:1 ~ 3:1.
The mole number of above-mentioned paraformaldehyde be certain quality under, the mole number converting out according to the molecular weight of formaldehyde.
Preferably, the polymerization degree of described paraformaldehyde is 10 ~ 100.
Preferably, step a) described in organic solvent be toluene, ethylbenzene or dimethylbenzene.
Preferably, step a) in temperature of reaction be 50 DEG C.
Preferably, step b) described in soaking time be 3 hours.
Preferably, step b) described in alkali lye be sodium hydroxide solution or potassium hydroxide solution.
Preferably, steps d) described in acidity regulator be oxalic acid or acetic acid.
Preferably, steps d) in the method for removing organic solvent be first carry out air distillation, then carry out underpressure distillation, vacuum tightness during underpressure distillation is higher than 0.8MPa.
Advantage of the present invention substitutes formalin with paraformaldehyde, feeds intake simple, dangerous reduction.Employing toluene is solvent, and can remove moisture in product when distilling, effectively reduce the moisture content of product, by adding alkylphenol, the water-absorbent of product is low, and volatility is low, and synthesis reaction temperature is low, and process is simple.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not only confined to embodiment.
Embodiment 1:
By p-cresol 840kg, toluene 735L, paraformaldehyde 249kg drop in reactor, stir half an hour, are warming up to 40 DEG C, drip sodium hydroxide solution 60.5kg, drip after terminating and are incubated 2 hours at 50 DEG C, be warming up to 80 DEG C, be incubated 3 hours after insulation terminates; Be cooled to less than 80 DEG C, add oxalic acid 15kg, stir 30 minutes; Drop into Resorcinol 642kg, be warming up to 110 DEG C of backflows, react 5 hours; air distillation removing toluene, to still temperature about 150 DEG C, starts underpressure distillation toluene; controlling vacuum tightness during decompression is higher than 0.08MPa; still temperature about 160 DEG C, sampling per hour detects softening temperature, starts tablets press when softening temperature reaches 99 DEG C; open material pump; adjusting rotary speed, to producing particle for semicircle, obtains finished product about 1600kg.
Embodiment 2:
By p-cresol 840kg, toluene 735L, paraformaldehyde 249kg drop in reactor, stir half an hour, are warming up to 50 DEG C, drip potassium hydroxide solution 60.5kg, drip after terminating and are incubated 2 hours at 55 DEG C, be warming up to 95 DEG C, be incubated 3 hours after insulation terminates; Be cooled to less than 80 DEG C, add oxalic acid 15kg, stir 30 minutes; Drop into Resorcinol 642kg, be warming up to 120 DEG C of backflows, react 5 hours; air distillation removing toluene is to still temperature about 150 DEG C; start underpressure distillation toluene, control vacuum tightness during decompression higher than 0.08MPa, still temperature about 160 DEG C; sampling per hour detects softening temperature; softening temperature starts tablets press when reaching 105 DEG C, opens material pump, adjusting rotary speed; to producing particle for semicircle, obtain finished product about 1600kg.
Embodiment 3:
By p-cresol 840kg, toluene 735L, paraformaldehyde 249kg drop in reactor, stirring half an hour, are warming up to 60 DEG C, drip potassium hydroxide 60.5kg, drip after terminating and are incubated 2 hours at 55 DEG C, be warming up to 100 DEG C, be incubated 3 hours after insulation terminates; Be cooled to less than 80 DEG C, add oxalic acid 15kg, stir 30 minutes; Drop into Resorcinol 642kg, be warming up to 100 DEG C of backflows, react 5 hours; air distillation removing toluene is to still temperature about 150 DEG C; start underpressure distillation toluene, controlling vacuum tightness during decompression is higher than 0.08MPa, still temperature about 160 DEG C; sampling per hour detects softening temperature; softening temperature starts tablets press when reaching 109 DEG C, opens material pump, adjusting rotary speed; to producing particle for semicircle, obtain finished product about 1600kg.
Embodiment 4:
By p-cresol 840kg, toluene 735L, paraformaldehyde 249kg drop in reactor, stirring half an hour, are warming up to 70 DEG C, drip sodium hydroxide 60.5kg, drip after terminating and are incubated 2 hours at 50 DEG C, be warming up to 90 DEG C, be incubated 3 hours after insulation terminates; Be cooled to less than 80 DEG C, add oxalic acid 15kg, stir 30 minutes; Drop into Resorcinol 642kg, be warming up to 110 DEG C of backflows, react 5 hours; air distillation removing toluene is to still temperature about 150 DEG C; start underpressure distillation toluene, controlling vacuum tightness during decompression is higher than 0.08MPa, still temperature about 160 DEG C; sampling per hour detects softening temperature; softening temperature starts tablets press when reaching 100 DEG C, opens material pump, adjusting rotary speed; to producing particle for semicircle, obtain finished product about 1600kg.
Embodiment 5:
By p-cresol 840kg, toluene 735L, paraformaldehyde 249kg drop in reactor, stirring half an hour, are warming up to 55 DEG C, drip sodium hydroxide 60.5kg, drip after terminating and are incubated 2 hours at 55 DEG C, be warming up to 95 DEG C, be incubated 3 hours after insulation terminates; Be cooled to less than 80 DEG C, add oxalic acid 15kg, stir 30 minutes; Drop into Resorcinol 642kg, be warming up to 120 DEG C of backflows, react 5 hours; air distillation removing toluene is to still temperature about 150 DEG C; start underpressure distillation toluene, controlling vacuum tightness during decompression is higher than 0.08MPa, still temperature about 160 DEG C; sampling per hour detects softening temperature; softening temperature starts tablets press when reaching 105 DEG C, opens material pump, adjusting rotary speed; to producing particle for semicircle, obtain finished product about 1600kg.
Last it is noted that above embodiment only in order to illustrate the present invention and and unrestricted technical scheme described in the invention; Therefore, although this specification sheets with reference to each above-mentioned embodiment to present invention has been detailed description, those of ordinary skill in the art should be appreciated that and still can modify to the present invention or equivalent to replace; And all do not depart from technical scheme and the improvement thereof of the spirit and scope of the present invention, it all should be encompassed in right of the present invention.
Claims (6)
1. a preparation method for modified rubber tackiness agent resorcinol formaldehyde resin, is characterized in that, comprises the steps:
A) will drop in organic solvent sylvan, paraformaldehyde, stir at 40 ~ 70 DEG C;
B) be incubated 1 ~ 4 hour after dripping alkali lye, the dripping quantity of alkali lye is 2 ~ 5% of paraformaldehyde mole number;
C) by step b) product heats to 80 ~ 100 DEG C that obtain, be incubated and be cooled to less than 90 DEG C after 2 ~ 4 hours;
D) in step c) add acidity regulator neutralization in the product that obtains, the dosage of described acidity regulator is 50% of alkali lye mole number, adds Resorcinol and be warming up to 100 ~ 150 DEG C of back flow reaction 2 ~ 5 hours after stirring;
E) by steps d) product that obtains removing organic solvent, start when product softening temperature is 99 ~ 109 DEG C to carry out granulation, obtain granular resorcinol formaldehyde resin;
Wherein, the polymerization degree of described paraformaldehyde is 10 ~ 100;
Wherein, the described mol ratio to sylvan and paraformaldehyde is 1:1 ~ 1:2;
Wherein, the mol ratio of described paraformaldehyde and Resorcinol is 1.5:1 ~ 3:1;
Wherein, step a) described in organic solvent be toluene, ethylbenzene or dimethylbenzene.
2. preparation method according to claim 1, is characterized in that, step a) in temperature of reaction be 50 DEG C.
3. preparation method according to claim 1, is characterized in that, step b) described in soaking time be 3 hours.
4. preparation method according to claim 1, is characterized in that, step b) described in alkali lye be sodium hydroxide solution or potassium hydroxide solution.
5. preparation method according to claim 1, is characterized in that, steps d) described in acidity regulator be oxalic acid or acetic acid.
6. preparation method according to claim 1, is characterized in that, steps d) in the method for removing organic solvent be first carry out air distillation, then carry out underpressure distillation, vacuum tightness during underpressure distillation is higher than 0.8MPa.
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| CN201410188527.1A CN103936952B (en) | 2014-05-06 | 2014-05-06 | A kind of preparation method of modified rubber tackiness agent resorcinol formaldehyde resin |
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| CN201410188527.1A CN103936952B (en) | 2014-05-06 | 2014-05-06 | A kind of preparation method of modified rubber tackiness agent resorcinol formaldehyde resin |
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| CN108129622A (en) * | 2017-12-22 | 2018-06-08 | 江苏国立化工科技有限公司 | The preparation method of alkylation modification phenolic resin tackifier |
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| CN103554394A (en) * | 2013-10-16 | 2014-02-05 | 科迈化工股份有限公司 | Synthetic method of modified resorcinol rubber adhesive |
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| CN103554394A (en) * | 2013-10-16 | 2014-02-05 | 科迈化工股份有限公司 | Synthetic method of modified resorcinol rubber adhesive |
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Effective date of registration: 20160202 Address after: 200010 Shanghai City Huang Road No. 18 10 floor Applicant after: Shanghai Lucky Biological & Chemical Technology Co., Ltd. Applicant after: Shanghai Ruinian Fine Chemical Co., Ltd. Address before: 201512 Shanghai Jinshan District City Industrial Zone second Sea Road No. 588 Applicant before: Shanghai Ruinian Fine Chemical Co., Ltd. |
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