CN1733816A - Alkyl resorcinol formaldehyde resin and its production process - Google Patents
Alkyl resorcinol formaldehyde resin and its production process Download PDFInfo
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- CN1733816A CN1733816A CN 200510046538 CN200510046538A CN1733816A CN 1733816 A CN1733816 A CN 1733816A CN 200510046538 CN200510046538 CN 200510046538 CN 200510046538 A CN200510046538 A CN 200510046538A CN 1733816 A CN1733816 A CN 1733816A
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Abstract
The invention provides an alkyl resorcinol formaldehyde resin for the production of rubber products including tires and wire rope conveying belts, as well as the production process. The resin comprises the following substances: resorcinol 22-25 parts, formaldehyde 10-11.5 parts, phenylethene 11-13 parts, oxalic acid 0.5-0.8 part, water 8-12 parts, and 20% of NaOH solvent. The production process comprises alkylation reaction and hydroxylation.
Description
Technical field
The invention belongs to the Chemical Manufacture raw material, particularly a kind ofly produce alkyl resorcinol formaldehyde resin and the production technique that rubber items such as tire, steel-cord conveyor belt are used.
Technical background
At present, rubber items such as domestic production tire, steel-cord conveyor belt, used additive is Resorcinol, resorcinol formaldehyde resin (RF), exists the difficult problem of pollution and product bloom in process of production.When with Resorcinol or Resorcinol and other organic or inorganic carrier compound as donor, give structure with methylene radical in the sizing material and become the direct binding system of HRH, play the adhesive effect of rubber and nylon cord, Steel Wire Surface, but carrying out in the mixing process with rubber, with produce Resorcinol distillation, be fuming, thereby generate irritating smoke pollution of environment; Simultaneously, contain a certain amount of free Resorcinol in the product, make product cause the bloom phenomenon, influence the quality of product.
Summary of the invention
The objective of the invention is to overcome above-mentioned technical deficiency, a kind of pollution-free, no bloom, the alkyl resorcinol formaldehyde resin that can improve the quality of products and production technique are provided.
The technical scheme that technical solution problem of the present invention adopts is: alkyl resorcinol formaldehyde resin is made up of six kinds of materials: 22～25 parts of Resorcinols, 10～11.5 parts in formaldehyde, 11～13 parts of vinylbenzene, 0.5～0.8 part of oxalic acid, 8～12 parts in water, 20% NaOH solution, through alkylated reaction, hydroxylation reaction, its molecular formula:
First kind of technology of the production of this resin is: add 25 parts of Resorcinols in reaction flask, after intensification is heated to fine melt, add 0.6 part of oxalic acid down in 100 ℃ of-130 ℃ of stirrings, begin to drip 10.5 parts of vinylbenzene when being warming up to 120-125 ℃, after dripping off in 30 minutes, kept this thermotonus 30 minutes, and under agitation in the time of 100-105 ℃, began to drip 11 parts of formaldehyde solutions again, dripped off in one hour, back flow reaction is 3 minutes again, heat up then and dewater, water added 25 parts of vinylbenzene after taking off to the greatest extent again, in 120-125 ℃ of reaction 30 minutes, and then after being neutralized into neutrality with 20% the NaOH aqueous solution, distillation dehydration is removed small molecules, controls the product softening temperature at 90-120 ℃, free phenol 0.6%; Second kind of technology is: add 25 parts of Resorcinols in reaction flask, 10 parts in water, be warming up to dissolving, under agitation add 0.65 part of oxalic acid, begin to drip 11.5 parts in formaldehyde when being warming up to 90 ℃, temperature control 90-110 ℃, after dripping off formaldehyde, the intensification distillation dehydration is when temperature reaches 120 ℃, beginning drip styrene 11 minutes, and temperature control 120-130 ℃ reacted 30 minutes after dripping off again, adds after 20% NaOH solution is neutralized into neutrality, and most water and small molecules are taken off in redistillation, control the product softening temperature at 103 ℃, free phenol 0.95%; The third technology is: added Resorcinol 22 minutes in reaction flask, be warming up to fusing, add 0.63 part of oxalic acid during to 120 ℃, then in 9.5 parts of 120-130 ℃ of drip styrenes, drip off the back in this thermotonus 30 minutes, when being cooled to 110 ℃, drip 10 parts in formaldehyde and drip off the back in 100-105 ℃ of reaction one hour 30 minutes, the dehydration that heats up, water drips 2.2 parts of vinylbenzene after taking off to the greatest extent again when temperature reaches 125 ℃, and in this thermotonus after 30 minutes, after NaOH with 20% was neutralized into neutrality, the intensification distillation dehydration was when 115 ℃ of softening temperatures, blowing is surveyed free m-phthalic acid 0.45%
The invention has the beneficial effects as follows: when adopting this resin as rubber items such as production tire, steel-cord conveyor belts, pollution-free in the production process, no bloom, and improved quality product.
Embodiment
Embodiment one: in the 500ml reaction flask, add Resorcinol 250g, after intensification is heated to fine melt, in about 115 ℃, stir and add 6g oxalic acid down, begin drip styrene when being warming up to 120-125 ℃, after dripping off 105g vinylbenzene in about 30 minutes, kept this thermotonus 30 minutes, under agitation begin to drip formaldehyde solution 110g again in the time of 100-105 ℃, dripped off in about 1 hour, back flow reaction is 30 minutes again, dehydration then heats up, add 25g vinylbenzene after water takes off to the greatest extent again in 120-125 ℃ of reaction 30 minutes, be neutralized into neutrality with the aqueous solution of 20% NaOH then after, distillation dehydration and remove small molecules, control product softening temperature is qualified at 90-120 ℃, 109 ℃ of this experiment product softening temperatures, free phenol 0.6%, output 385g.
Embodiment two: in the 500ml reaction flask, add Resorcinol 250g water 100g and be warming up to dissolving, under agitation add oxalic acid 6.5g, when being warming up to 90 ℃, begin to drip formaldehyde 115g, temperature control 90-110 ℃ drip off formaldehyde after, the intensification distillation dehydration, when room temperature reaches 120 ℃, the beginning drip styrene, and temperature control 120-130 ℃ reacted 30 minutes after dripping off 110g vinylbenzene again, after the NaOH solution of adding 20% was neutralized into neutrality, most water and small molecules were taken off in redistillation, surveyed 103 ℃ of softening temperatures, free phenol 0.95%, output 370g.
Embodiment three: in the reaction flask of 500ml, input 220g Resorcinol is warming up to and dissolves, add oxalic acid 6.3g in 120 ℃, then in 120-130 ℃ of drip styrene 95g, drip off the back in this thermotonus 30 minutes, when being cooled to 110 ℃, dripping a formaldehyde 100.3g and drip off the back in 100-105 ℃ of reaction 1 hour 30 minutes, dehydration heats up, after water takes off to the greatest extent when temperature reaches 125 ℃ drip styrene 22g again, and in this thermotonus after 30 minutes, after the NaOH with 20% is neutralized into neutrality, the intensification distillation dehydration, softening temperature is surveyed in sampling, when 115 ℃ of softening temperatures, and blowing, survey free Resorcinol 0.45%, output 345g.
The free Resorcinol of alkyl resorcinol formaldehyde resin and RF resin is more as shown in table 1: table 1
| Kind | The RF resin | Embodiment one | Embodiment two | Embodiment three |
| Free Resorcinol (%) | ＞18 | 0.6 | 0.95 | 0.45 |
So this product is a kind of raising rubber item quality, help the alkylresorcinol resins of environment protection.
Claims (2)
1, a kind of alkyl resorcinol formaldehyde resin, it is characterized in that forming: 22～25 parts of Resorcinols, 10～11.5 parts in formaldehyde, 11～13 parts of vinylbenzene, 0.5～0.8 part of oxalic acid by following six kinds of materials, 8～12 parts in water, 20% NaOH solution, through alkylated reaction, hydroxylation reaction, its molecular formula:
2, the production technique of alkyl resorcinol formaldehyde resin according to claim 1 is characterized in that:
A, in reaction flask, add 25 parts of Resorcinols, after intensification is heated to fine melt, add 0.6 part of oxalic acid down in 100 ℃ of-130 ℃ of stirrings, begin to drip 10.5 parts of vinylbenzene when being warming up to 120-125 ℃, after dripping off in 30 minutes, kept this thermotonus 30 minutes, and under agitation in the time of 100-105 ℃, began to drip 11 parts of formaldehyde solutions again, dripped off in one hour, back flow reaction is 30 minutes again, heat up then and dewater, water added 25 parts of vinylbenzene after taking off to the greatest extent again, in 120-125 ℃ of reaction 30 minutes, and then after being neutralized into neutrality with 20% the NaOH aqueous solution, distillation dehydration is removed small molecules, controls the product softening temperature at 90-120 ℃, free phenol 0.6%;
B, add 25 parts of Resorcinols in reaction flask, 10 parts in water is warming up to dissolving, under agitation add 0.65 part of oxalic acid, begin to drip 11.5 parts in formaldehyde when being warming up to 90 ℃, temperature control 90-110 ℃, after dripping off formaldehyde, the intensification distillation dehydration is when temperature reaches 120 ℃, beginning drip styrene 11 minutes, and temperature control 120-130 ℃ reacted 30 minutes after dripping off again, adds after 20% NaOH solution is neutralized into neutrality, and most water and small molecules are taken off in redistillation, control the product softening temperature at 103 ℃, free phenol 0.95%;
C, in reaction flask, added Resorcinol 22 minutes, be warming up to fusing, add 0.63 part of oxalic acid during to 120 ℃, then in 9.5 parts of 120-130 ℃ of drip styrenes, drip off the back in this thermotonus 30 minutes, when being cooled to 110 ℃, drip 10 parts in formaldehyde and drip off the back in 100-105 ℃ of reaction one hour 30 minutes, the dehydration that heats up, water drips 2.2 parts of vinylbenzene after taking off to the greatest extent again when temperature reaches 125 ℃, and in this thermotonus after 30 minutes, after NaOH with 20% was neutralized into neutrality, the intensification distillation dehydration was when 115 ℃ of softening temperatures, blowing is surveyed free m-phthalic acid 0.45%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100465387A CN100487012C (en) | 2005-05-27 | 2005-05-27 | Alkyl resorcinol formaldehyde resin and its production process |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100465387A CN100487012C (en) | 2005-05-27 | 2005-05-27 | Alkyl resorcinol formaldehyde resin and its production process |
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| CN1733816A true CN1733816A (en) | 2006-02-15 |
| CN100487012C CN100487012C (en) | 2009-05-13 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235165B (en) * | 2007-08-01 | 2010-08-11 | 华奇（张家港）化工有限公司 | M-aminophenol modified aralkylresorcinol-aldehydes compound resin used for rubber formulation and application |
| CN102718934A (en) * | 2012-06-14 | 2012-10-10 | 北京彤程创展科技有限公司 | Cashew nut shell oil modified resorcinol bonding resin and preparation method thereof |
| CN103087284A (en) * | 2012-11-14 | 2013-05-08 | 江苏国立化工科技有限公司 | Preparation method of alkylresorcinol formaldehyde resin |
| CN103113541A (en) * | 2012-12-19 | 2013-05-22 | 山东沾化奥仕化学有限公司 | Resorcinol aldehyde resin formed by modification of olefin and aromatic hydrocarbon and production process thereof |
| CN103289036A (en) * | 2013-06-04 | 2013-09-11 | 山东阳谷华泰化工股份有限公司 | Production method of resorcinol formaldehyde resin |
| CN113621119A (en) * | 2020-05-06 | 2021-11-09 | 华奇（中国）化工有限公司 | Xylene-modified resorcin aldehyde resin and rubber composition thereof |
-
2005
- 2005-05-27 CN CNB2005100465387A patent/CN100487012C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235165B (en) * | 2007-08-01 | 2010-08-11 | 华奇（张家港）化工有限公司 | M-aminophenol modified aralkylresorcinol-aldehydes compound resin used for rubber formulation and application |
| CN102718934A (en) * | 2012-06-14 | 2012-10-10 | 北京彤程创展科技有限公司 | Cashew nut shell oil modified resorcinol bonding resin and preparation method thereof |
| CN102718934B (en) * | 2012-06-14 | 2014-10-29 | 北京彤程创展科技有限公司 | Cashew nut shell oil modified resorcinol bonding resin and preparation method thereof |
| CN103087284A (en) * | 2012-11-14 | 2013-05-08 | 江苏国立化工科技有限公司 | Preparation method of alkylresorcinol formaldehyde resin |
| CN103113541A (en) * | 2012-12-19 | 2013-05-22 | 山东沾化奥仕化学有限公司 | Resorcinol aldehyde resin formed by modification of olefin and aromatic hydrocarbon and production process thereof |
| CN103289036A (en) * | 2013-06-04 | 2013-09-11 | 山东阳谷华泰化工股份有限公司 | Production method of resorcinol formaldehyde resin |
| CN103289036B (en) * | 2013-06-04 | 2015-08-26 | 山东阳谷华泰化工股份有限公司 | A kind of production method of resorcinol formaldehyde resin |
| CN113621119A (en) * | 2020-05-06 | 2021-11-09 | 华奇（中国）化工有限公司 | Xylene-modified resorcin aldehyde resin and rubber composition thereof |
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| CN100487012C (en) | 2009-05-13 |
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