CN105085849B - A kind of modified resorcinol formaldehyde resin adhesion promotor and preparation method thereof - Google Patents
A kind of modified resorcinol formaldehyde resin adhesion promotor and preparation method thereof Download PDFInfo
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- CN105085849B CN105085849B CN201510462756.2A CN201510462756A CN105085849B CN 105085849 B CN105085849 B CN 105085849B CN 201510462756 A CN201510462756 A CN 201510462756A CN 105085849 B CN105085849 B CN 105085849B
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Abstract
The invention discloses modified resorcinol formaldehyde resin adhesion promotor of a kind of phenolic acid and preparation method thereof, resorcinol formaldehyde resin, acidic catalyst are added into reactor, agitating heating is molten into liquid, after being slowly added dropwise in modifying agent, reactor when reacting 12；It is further continued for being slowly added dropwise formalin, reacts 0.5 1.5 hours；Air-distillation, after evacuation dehydration and other volatile substances, obtains the modified adhesion promotor of phenolic acid.The modified adhesion promotor that the present invention is provided, while technique is improved, by multiple functional groups of phenolic acid, enhances stereo crosslinked network structure, reduces free resorcinol content, improves intensity, bond propertiess and the ageing-resistant performance of resin.Its preparation method improves production efficiency, and realizes environmental protection, energy-saving and emission-reduction green production.
Description
Technical field
The present invention relates to rubber industry field, and in particular to a kind of modified resorcinol formaldehyde resin adhesion promotion of phenolic acid
The preparation method and applications of agent, the application particularly in rubber composition.
Background technology
Polyester, steel wire etc. are commonly used in tyre industry as skeleton reinforcing material, for increasing the intensity of rubber.
But due to there is huge nature difference between rubber and steel wire, combination between the two has huge to the final performance of material
Impact.Rubber and all-steel cord form good mechanical engagement in sulfidation and can obtain excellent initial viscosity, but by
In aging and rubber use, bond propertiess often weaken or are wholly absent, and cause to bond premature failure.In order to keep away
Exempt from such case, be usually added into adhesion promotor rubber or rubber composition to be maintained with the excellent adhesion between metal.
Between rubber and all-steel cord promotion bonding, traditional method be using bi-component binding system, will methylene
Among donor and methylene receptor are added to rubber simultaneously, during vulcanisation step, both react to form cross-linked network
Network, improves physical property, the mechanical performance of rubber；The generation effect between rubber and steel wire simultaneously, improves rubber and steel wire
Between interact and finally improve both adhesion.
As methylene receptor, it is necessary to there is higher reactivity, could discharge with methylene donor rapidly
The methylene reaction for coming, forms cross-linked network, in rubbery parent substance so as to improve the adhesion between rubber and steel wire.Often at present
The methylene receptor seen includes resorcinol, resorcin phenolic resin, metacresol phenolic resin, phenol formaldehyde resin, alkane
Base phenol-resorcinol formaldehyde resin etc. is various.The wherein reactivity highest of resorcinol and methylene donor, using isophthalic
Diphenol is as jointing material for the adhesion between raising rubber and steel wire has remarkable result.Resorcinol formaldehyde resin is rubber
The conventional all-steel cord of glue tire industry and the binding agent between polyester cord and rubber.
But resorcinol is a kind of small molecule of easy distillation, between unreacted free in resorcinol formaldehyde resin
Its volatility of Benzodiazepiness and smokiness are very serious, under rubber processing conditions, easily bring harm, Er Qieyin to environment and human body
Distillation is also resulted in measures inaccurate, and the performance of product is had a negative impact.
For this purpose, develop the processing method of many resorcinol or resorcin phenolic resin, with reduce it is free between
Benzodiazepiness, reduce the purpose of smoke and loss of weight in use.
For example, CN101220130A provides a kind of method by the aqueous solution of saliferous, resorcinol, formaldehyde and has 3 to 6
The aliphatic ketone of carbon atom carries out polyreaction in the presence of acidic, and resorcin/formaldehyde resin is obtained.The method exists
The content that Benzodiazepiness are sowed discord in product middle reaches is reduced to a certain extent, but such product can also produce smog in refining glue, damage
Healthy and pollution environment, product still suffer from hygroscopicity, are easy to the problem of caking.
A kind of steel cord adhesive for radial tyre that CN1858141 is provided and preparation method thereof, makes resorcinol
It is polymerized under base catalyst effect with bisphenol A epoxide resin, obtains resorcinol-bisphenol a resin, then act in acidic catalyst
Under, it is modified using melamine monomer, obtain tripolycyanamide-resorcinol-bisphenol A epoxide resin.But modified is with double
The bisphenol A epoxide resin of etherification reaction group, thus etherification reaction can form high polymer, molecular weight crosses conference causes gained resin
It is difficult to dispersed in rubbery system.To control the generation of high polymer, the reaction can not be carried out thoroughly, so remaining on
With a certain amount of free resorcinol, smoke and loss of weight problem are yet suffered from.
CN101235165A provides a kind of m-aminophenol modified aralkyl resorcinol-aldehydes compound resin, plus
Enter mechanical performance, the bond propertiess of aging and unaged rubber that the resin can improve vulcanite or rubber composition, together
When improve smoke problem.But as which is two-step reaction, and often step reaction all needs to use longer time, therefore reaction time
The long, shortcoming of high energy consumption is unfavorable for industrialized production.
The content of the invention
For the deficiencies in the prior art, the present invention provides a kind of phenolic acid modified resorcinol formaldehyde resin adhesion promotion
Agent, while providing its preparation method.
The present invention is achieved through the following technical solutions：
The modified resorcinol formaldehyde resin adhesion promotor of a kind of phenolic acid, with following general structure：
Wherein x, y are greater than the integer equal to 1, and m, n are the integers of 0-50.
Wherein R1、R2、R3Each that independent is H, OH or OR4, wherein R4It is the alkyl or aromatic radical of 1-12 carbon atom
Group.
A kind of preparation method of the modified resorcinol formaldehyde resin adhesion promotor of phenolic acid, comprises the following steps：
（1）During resorcinol formaldehyde resin resin is placed in the reactor equipped with mechanical agitator, heating is molten into liquid
Body, adds acidic catalyst mix homogeneously；
（2）Feed temperature in reactor is increased to into 110-150 DEG C, modifying agent, resorcinol formaldehyde tree is slowly added dropwise
Fat is 100 with the mass ratio of modifying agent:0.1-50, time for adding 20-30 minutes, continues stirring reaction 1-2 hour；
（3）Formalin is slowly added dropwise under stirring, resorcinol formaldehyde resin with the mass ratio of formalin is
100：1-50, reacts 0.5-1.5 hours；
（4）To in above-mentioned mixed liquor add alkaline matter in and acidic catalyst；
（5）Air-distillation, evacuation dehydration, devolatilization material, obtains resorcinol formaldehyde resin adhesion promotor.
Described modifying agent is the phenolic acid compound containing double bond structure.
Specific course of reaction is as follows：
In preparation method,
The phenolic acid compound containing double bond structure, it is preferred that at least containing the phenolic acids chemical combination shown in formula (1)
Thing,
(1)
Wherein R1、R2、R3Each that independent is H, OH or OR4, wherein R4It is the alkyl or aromatic group of 1-12 carbon atom； n、
M is the integer of 0-50, and preferred n, m are the integers of 0-20.
The phenolic acid compound containing double bond structure includes caffeic acid, ferulic acid, vanillic acid, sinapic acid, chlorogenic acid
In one or more.
The acid catalyst is p-methyl benzenesulfonic acid, DBSA, acid dimethyl, benzenesulfonic acid, hydrochloric acid, sulfur
One or more in acid, phosphoric acid.
The alkaline matter is sodium hydroxide, potassium hydroxide, triethylamine, triethanolamine, one or more in ammonium acetate
Aqueous solution, mass percent concentration is 10-20%.
Modified resorcinol-application of the aldehydes adhesion promotor in rubber of a kind of phenolic acid, especially in tire
Using.
The present invention has advantages below：
A kind of modified adhesion promotor that the present invention is provided, it is most important that using a kind of phenolic acids with reactivity
Material is modified to resorcinol formaldehyde resin, while technique is improved, by multiple functional groups of phenolic acid, is increased
Strong stereo crosslinked network structure, reduces free resorcinol content, improves intensity, bond propertiess and the resistance to ag(e)ing of resin
Can, the modified resorcinol formaldehyde resin more excellent so as to obtain performance.
The production method of the modified resorcinol formaldehyde resin that the present invention is provided improves production efficiency, and realizes ring
Guarantor, energy-saving and emission-reduction green production.
Specific embodiment
Again the above of the present invention is described in further detail below by embodiment, but this should not be understood
Scope for above-mentioned theme of the invention is only limitted to below example.
Embodiment 1
（1）Resorcinol formaldehyde resin 100g is placed in and is leaked equipped with mechanical agitator, thermometer, reflux condenser and dropping liquid
In in the 500ml reactors of bucket, heating is molten into liquid；Add 0.2g p-methyl benzenesulfonic acid mix homogeneously；
（2）Temperature of reaction kettle is increased to into 140 DEG C, and in above-mentioned mixed liquor, Deca ferulic acid 2g, time for adding 20-
30 minutes, material in reactor continued reaction 1 hour, and is stirred continuously；
（3）The formalin 3g that mass percent concentration is 37% is slowly added dropwise under stirring, is reacted 0.5 hour；
（4）To in above-mentioned mixed liquor add mass percent concentration be 10% NaOH in and acidic catalyst, make Ph be 7
Left and right；
（5）Then thick liquid in reactor is poured out, between obtaining by air-distillation, evacuation dehydration, devolatilization material
Resorcinol formaldehyde resin-bonding accelerator.
Embodiment 2
（1）Resorcinol formaldehyde resin 100g is placed in and is leaked equipped with mechanical agitator, thermometer, reflux condenser and dropping liquid
In in the 500ml reactors of bucket, heating is molten into liquid；Add 0.3g acid dimethyl mix homogeneously；
（2）Temperature of reaction kettle is increased to into 140 DEG C, and in above-mentioned mixed liquor, Deca ferulic acid 5g, time for adding 20-
30 minutes, continue reaction 1.5 hours in reactor, and be stirred continuously；
（3）The formalin 3g that mass percent concentration is 37% is slowly added dropwise under stirring, is reacted 0.5 hour；
（4）To in above-mentioned mixed liquor add mass percent concentration be 10% NaOH in and acidic catalyst, make Ph be 7
Left and right；
（5）Then thick liquid in reactor is poured out, between obtaining by air-distillation, evacuation dehydration, devolatilization material
Resorcinol formaldehyde resin-bonding accelerator.
Embodiment 3
（1）Resorcinol formaldehyde resin 100g is placed in and is leaked equipped with mechanical agitator, thermometer, reflux condenser and dropping liquid
In in the 500ml reactors of bucket, heating is molten into liquid；Add 0.5g mixed in hydrochloric acid uniform；
（2）Temperature of reaction kettle is increased to into 140 DEG C, and in above-mentioned mixed liquor, Deca vanillic acid 7g, time for adding 20-
30 minutes, continue reaction 2 hours in reactor, and be stirred continuously；
（3）The formalin 4g that mass percent concentration is 37% is slowly added dropwise under stirring, is reacted 0.5 hour；
（4）To in above-mentioned mixed liquor add mass percent concentration be 10% NaOH in and acidic catalyst, make Ph be 7
Left and right；
（5）Then thick liquid in reactor is poured out, between obtaining by air-distillation, evacuation dehydration, de- other materials
Resorcinol formaldehyde resin-bonding accelerator.
The contrast experiment of 4 bond propertiess of embodiment
According to standard GB/T 3513-2001, bond propertiess experiment is carried out.Bond propertiess are carried out with reference to the formula of following table 1
Experiment, to the bond propertiess for checking binder resin.Following formula is conventional truck bias tyre steel bead wire Rubbering formula.
1 bond propertiess experimental formula of table
| Raw material | Formula 1# | Formula 2# | Formula 3# |
| Natural rubber | 30.00 | 30.00 | 30.00 |
| Butadiene-styrene rubber | 70.00 | 70.00 | 70.00 |
| White carbon black N660 | 40.00 | 40.00 | 40.00 |
| White carbon black N330 | 30.00 | 30.00 | 30.00 |
| White carbon | 6.00 | 6.00 | 6.00 |
| Aromatic naphtha | 30.00 | 30.00 | 30.00 |
| Stearic acid | 1.00 | 1.00 | 1.00 |
| Zinc Oxide | 10.00 | 10.00 | 10.00 |
| Insoluble sulfuy HDOT20 | 5.00 | 5.00 | 5.00 |
| Accelerator NS | 1.00 | 1.00 | 1.00 |
| Anti-aging agent RD | 1.00 | 1.00 | 1.00 |
| Antioxidant 4010NA | 1.00 | 1.00 | 1.00 |
| Binding agent RA | 5.00 | 5.00 | 5.00 |
| New cobalt decanoate LC-D20 | 1.00 | 1.00 | 1.00 |
| Other | 10.00 | 10.00 | 10.00 |
| A | 2.00 | ||
| B | 2.00 | ||
| C | 2.00 |
Note：A is phenol-formaldehyde resin（The emerging Industrial Co., Ltd.'s product of upper sea water）
B is unmodified resorcinol-formaldehyde resin（Tianjin Huan Qi International Trading Company Ltd product）
C is the resorcinol-formaldehyde resin that phenolic acid is modified（1,2 or 3 product of embodiment）
Experimental result is shown in Table 2.
2 bond propertiess experimental result of table
| Performance indications | Formula 1# | Formula 2# | Formula 3# |
| Shao Er A type hardness testers/degree | 71 | 72 | 74 |
| 100% stress at definite elongation/Mpa | 4.12 | 4.34 | 4.36 |
| 300% stress at definite elongation/Mpa | 17.2 | 16.9 | 18.4 |
| Tensile strength/Mpa | 24.2 | 26.3 | 26.5 |
| Elongation rate of tensile failure/% | 459 | 441 | 437 |
| Aging front steel wire extraction/N | 826 | 987 | 1022 |
| Aging front rubber coating rate/% | 83 | 92 | 92 |
| Aging rear steel wire extraction/N | 705 | 816 | 1075 |
| Aging rear rubber coating rate/% | 65 | 84 | 86 |
| Bonding strength/（kN·m-1） | 119.4 | 121.5 | 127.2 |
Note：Aging condition：100℃*48h
Use high performance liquid chromatography（HPLC）The free resorcinol in unmodified resorcinol formaldehyde resin for measuring
Content be 9.2%, the modified resorcinol formaldehyde resin of phenol-formaldehyde resin and phenolic acid is without free resorcinol.
By data above as can be seen that the bonding force of phenol-formaldehyde resin is significantly less than resorcinol formaldehyde resin, and
Bonding force after aging reduces obvious；And the modified resorcinol formaldehyde resin of phenolic acid with resorcinol formaldehyde tree
The bond propertiess that lipid phase is worked as, and without free resorcinol, it is more environmentally friendly.
For those skilled in the art, under the premise without departing from the principles of the invention, can also do
Go out the change of some selections with regard to component and match ratio etc., these still should be regarded as protection scope of the present invention.
Claims (9)
1. the resorcinol formaldehyde resin adhesion promotor that a kind of phenolic acid is modified, it is characterised in that with following general structure：
Wherein x, y are greater than the integer equal to 1, and m, n are the integers of 0-50.
2. the preparation method of the modified resorcinol formaldehyde resin adhesion promotor of a kind of phenolic acid, it is characterised in that including following step
Suddenly：
（1）During resorcinol formaldehyde resin is placed in the reactor equipped with mechanical agitator, heating is molten into liquid, adds
Acidic catalyst mix homogeneously；
（2）Feed temperature in reactor is increased to into 110-150 DEG C, modifying agent is slowly added dropwise, resorcinol formaldehyde resin with
The mass ratio of modifying agent is 100：0.1-50, time for adding 20-30 minutes, continues stirring reaction 1-2 hour；
（3）Formalin is slowly added dropwise under stirring, resorcinol formaldehyde resin is 100 with the mass ratio of formalin：
1-50, reacts 0.5-1.5 hours；
（4）To in above-mentioned mixed liquor add alkaline matter in and acidic catalyst；
（5）Air-distillation, evacuation dehydration, devolatilization material, obtains resorcinol formaldehyde resin adhesion promotor；
Described modifying agent is the phenolic acid compound containing double bond structure.
3. the preparation method as described in claim 2, it is characterised in that：The phenolic acid compound containing double bond structure, extremely
Less containing the phenolic acid compound shown in formula (1),
(1)
Wherein R1、R2、R3Each that independent is H, OH or OR4, wherein R4It is the alkyl or aromatic group of 1-12 carbon atom；n、
M is the integer of 0-50.
4. the preparation method as described in claim 3, it is characterised in that：N, m are the integers of 0-20.
5. the preparation method as described in claim 2, it is characterised in that：The phenolic acid compound containing double bond structure is
One or more in caffeic acid, ferulic acid, vanillic acid, sinapic acid, chlorogenic acid.
6. the preparation method as described in claim 2, it is characterised in that：Described acid catalyst is organic acid or mineral acid, or
The mixing of organic acid and mineral acid.
7. the preparation method as described in claim 2 or 6, it is characterised in that：Described acid catalyst be p-methyl benzenesulfonic acid, ten
One or more in dialkyl benzene sulfonic acids, acid dimethyl, benzenesulfonic acid, hydrochloric acid, sulphuric acid, phosphoric acid.
8. the preparation method as described in claim 2, it is characterised in that：The alkaline matter is organic base or inorganic base, or is had
Machine alkali and inorganic base mixing.
9. the preparation method as described in claim 2 or 8, it is characterised in that：The alkaline matter is sodium hydroxide, hydroxide
The aqueous solution of one or more in potassium, triethylamine, triethanolamine, ammonium acetate, mass percent concentration is 10-20%.
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| CN106700003B (en) * | 2016-12-23 | 2018-10-12 | 沈阳化工大学 | A kind of benzyl phosphoric acid copolymerization phenol formaldehyde (PF) Foamex and preparation method thereof |
| CN109705410A (en) * | 2018-12-28 | 2019-05-03 | 江苏麒祥高新材料有限公司 | A kind of rubber composition and its preparation process for bead wire belt |
| CN114672074B (en) * | 2020-12-24 | 2024-02-09 | 彤程新材料集团股份有限公司 | Rubber composition containing xylene modified phenolic resin and application thereof |
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| CN100489023C (en) * | 2002-12-13 | 2009-05-20 | 茵迪斯佩克化学公司 | Phenolic modified resorcinolic resins for rubber compound formula |
| BRPI0822778B1 (en) * | 2008-06-30 | 2020-04-07 | Pirelli | tire |
| 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 |
| CN102875754B (en) * | 2012-09-28 | 2015-05-27 | 北京彤程创展科技有限公司 | Modified resorcinol phenolic resin and preparation method thereof and rubber compound |
| CN103910840B (en) * | 2013-01-09 | 2016-08-03 | 华奇（中国）化工有限公司 | Resorcinol air aldehyde resin that Fructus anacardii diphenol is modified and its preparation method and application |
| 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 |
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