CN103183799B - Alkyl phenolic resin rubber tackifier and preparation method - Google Patents
Alkyl phenolic resin rubber tackifier and preparation method Download PDFInfo
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- CN103183799B CN103183799B CN201110451513.0A CN201110451513A CN103183799B CN 103183799 B CN103183799 B CN 103183799B CN 201110451513 A CN201110451513 A CN 201110451513A CN 103183799 B CN103183799 B CN 103183799B
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Abstract
An alkyl phenolic resin rubber tackifier of the invention has a molecular structure containing benzoxazole heterocyclic groups, and the benzoxazole heterocyclic groups are bonded into the molecules by forming ether bonds through etherification reactions between benzoxazole heterocyclic compounds with monoetherification reaction functional groups and alkylphenol. The tackifier can provide good viscosity for unvulcanized rubber materials. In addition, the alkyl phenolic resin rubber tackifier of the invention can also significantly improve the adhesive force between rubber materials and steel cord materials.
Description
Technical field
The invention belongs to rubber tackifier technical field, relate to a kind of Alkyl phenolic resin rubber tackifier and preparation method thereof.
Background technology
In order to the rubber item of obtained excellent property, unvulcanized gum material must have enough viscosity, is convenient to the making in technological process and storage.
Viscosity described herein refers to self adhesive capacity of unvulcanized gum material or and other adhesive capacity needing between the material that bonds.This viscosity plays a very important role in the technological process manufacturing rubber product.
In the production process of radial, rubber raw materials and Synergist S-421 95 are through evenly mixing before sulfuration, and make film and Cladding Steel cord, revulcanization is shaping.Therefore gum material needs good viscosity to meet the mutual bounding force between sizing material and the bounding force between sizing material and steel cord.
The material that can be used as rubber tackifier has numerous species.As aliphatics and aromatic hydrocarbon resin, coumarone resin, polyterpene resin, terpene phenolic, rosin and rosin derivative, alkyl phenolic resin, alkylphenol acetylene resin etc., all can be used as rubber tackifier.
Hydrocarbon resin is in general cheap than alkyl phenolic resin, but will reach equal viscosity, then its amount needed is often comparatively large, is approximately that three times of alkyl phenolic resin are even more.
The tendency reducing rubber item performance is had when quantity is larger, so alkyl phenolic resin is usually preferentially selected, because its consumption is less when retaining in the tackifier in rubber.
But, add alkyl phenolic resin tackifier and often reduce the bounding force of gum material to wire or other reinforcement materials.
For this reason, when the bounding force between rubber and reinforcement material becomes key factor, hydrocarbon resin sometimes still can be selected, can need the tackifier adding more amount in this case, thus can affect the quality of rubber item to a certain extent.Therefore, when formulating the technical recipe of radial, needing the pros and cons of choosing comprehensively each side, taking the scheme that relatively reasonable.
Therefore some rubber industries, such as radial industry, demand has the rubber tackifier product of better over-all properties urgently.
In order to address this problem preferably, many investigators have employed multiple method and have carried out study on the modification to alkyl phenolic resin.
US Patent No. 7772345 discloses the compound that a kind of use contains vinyl, such as vinylbenzene, alkyl phenolic resin tackifier is carried out to the method for modification.
US Patent No. 4146512 discloses one primary amine or secondary amine compound, such as morpholine and diethanolamine, alkyl phenolic resin tackifier is carried out to the method for modification.
US Patent No. 8030418 discloses one primary amine or secondary amine compound and alkyl phenolic resin and reacts, and then with epoxide reactive technique, alkyl phenolic resin tackifier is carried out to the method for modification further.
A kind of method that Chinese patent CN102131858 discloses primary amine or secondary amine compound, rosin, longer chain fatty acid carry out modification to alkyl phenolic resin tackifier.
Although prior art has multiple improvement to Alkyl phenolic resin rubber tackifier, the initial viscosity of gum material and lasting adhesiveness are all improved to some extent, but these improvement all also exist certain undesirable situation, mainly over-all properties is still not ideal enough, particularly there is no significant raising to the bounding force between gum material and steel cord.Therefore the place being worth improving is still had.
Summary of the invention
The object of the invention is to the deficiency overcoming above-mentioned prior art, a kind of Alkyl phenolic resin rubber tackifier with ideal effect is provided.
The present invention's benzothiazole heterogeneous ring compound with etherified response function group participates in the building-up reactions of alkyl phenolic resin, generates the Alkyl phenolic resin rubber tackifier containing benzothiazole heterocyclic group.This tackifier not only have the advantage of general Alkyl phenolic resin rubber tackifier, initial viscosity is large, consumption is less, and good persistent sticky can be kept, particularly the bounding force between gum material and steel cord material is increased significantly and act on, be conducive to preventing tyre bead from coming to nothing and the problem such as explosion.Use Alkyl phenolic resin rubber tackifier of the present invention to manufacture radial, when other condition is identical, the over-all properties of radial can be significantly improved.
Another object of the present invention is to the preparation method that a kind of abovementioned alkyl resol rubber tackifier is provided.
This purpose of the present invention realizes, and the method that can adopt has multiple.Such as, first part or all alkylphenol and the benzothiazole heterogeneous ring compound with etherified response function group can be reacted, its phenolic hydroxyl group carries out etherificate, make etherate monomer, and then the etherate monomer made mixed with remaining alkylphenol and carries out polycondensation with aldehyde, the alkyl phenolic resin needed for generation.For another example, also first alkylphenol and aldehyde can be carried out polycondensation and make resin, then this resin and the benzothiazole heterogeneous ring compound with etherified response function group are carried out etherification reaction, the alkyl phenolic resin needed for generation.
The molar ratio range of whole alkylphenol monomers that said etherate monomer is used with synthesis rubber tackifying resin of the present invention is 0.001-1: 1 herein, is 0.1-0.4: 1 preferably.
The benzothiazole heterogeneous ring compound with etherified response function group of the present invention, refer to the halogenated compound simultaneously in a molecule with benzothiazole heterocyclic group and etherified reactive behavior, or there is the compound of benzothiazole heterocyclic group and monocycle oxygen groups simultaneously.Such as but not limited to 2-chloromethylthiobenzene and thiazole, 2-chloroethylthio benzothiazole, chloromethyl benzotriazole, 2-epoxypropyl sulfo-benzothiazole etc.
Embodiment
Following embodiment can contribute to understanding the present invention, instead of the restriction to content of the present invention.
Embodiment 1:
Add in 500ml reaction flask tert-octyl phenol 82.4g (0.4mol) and 100g methyl alcohol, stir and be slowly warming up to 65 DEG C, respectively by dropping funnel and screw feeder, drip the sodium hydrate methanol solution 106.7g (0.4mol) of 15% simultaneously respectively equably and add 2-chloromethylthiobenzene and thiazole 86.2g (0.4mol), the scope keeping pH value is between 9-11, feed time about 120 minutes.Continue after reinforced to stir insulation 60 minutes.Then heat up and steam methyl alcohol, when distillation temperature reaches 110 DEG C, keep half an hour.Then be down to room temperature, then be etherate monomer A of the present invention after washing, filtration, drying.
Embodiment 2:
Add in 1000ml reaction flask tert-octyl phenol 82.4g (0.4mol), etherificate monomer A 38.5g (0.1mol), toluene 40ml, 36% hydrochloric acid 1g.Open the water of condensation of return line, stir and heat up, when material rises to about 85 DEG C, have backflow phenomenon to produce.Keep backflow situation and Keep agitation, from addition funnel, drip the formalin 34g (0.42mol) of 37%, time for adding is about 30 minutes.After dripping formaldehyde, continue stirring and refluxing 180 minutes, then use in the aqueous sodium hydroxide solution of 20% and material extremely neutrality.Add toluene 90ml, stir 20 minutes, stratification, isolates aqueous phase.Add 100ml water again, be incubated 70 DEG C and stir 20 minutes, stratification, isolates aqueous phase again.Continue to stir and heat up, steam toluene and residual water-content, when material temperature rises to 160 DEG C, start vacuum, remove remaining water and toluene further, the highest distillation temperature is no more than 170 DEG C.Obtain the resin of yellow transparent, obtain finished product flaky resin by granulation.
Embodiment 3:
Add in 1000ml reaction flask tert-octyl phenol 72.1g (0.35mol), etherificate monomer A 57.8g (0.15mol), toluene 40ml, 36% hydrochloric acid 1g.Open reflux condensation mode water, stir and heat up, when material rises to about 85 DEG C, have backflow phenomenon to produce.Keep backflow and stir, from addition funnel, dripping the formalin 34g (0.42mol) of 37%, time for adding about 30 minutes.Continue stirring and refluxing 180 minutes after dripping formaldehyde, be then neutralized to neutrality with the aqueous sodium hydroxide solution of 20%.Add toluene 90ml, stir 20 minutes, stratification, isolates aqueous phase.Add 100ml water again, be incubated 70 DEG C, stir 20 minutes, stratification, isolates aqueous phase again.Continue to stir and heat up, steam toluene and residual water-content, when material temperature rises to 160 DEG C, start vacuum, remove remaining water and toluene further, the highest distillation temperature is no more than 170 DEG C.Obtain the resin of yellow transparent, obtain finished product flaky resin by granulation
The product of gained in embodiment is carried out Physico-chemical tests and performance test, and contrast with the commercially available prod p-tert-butylphenol acetylene resin rubber tackifier Koresin of commercially available prod to t-Octylphenol formaldehyde resin rubber tackifier SP-1068 and BASF AG of Schenectady international corporation of the U.S., the results are shown in table 1, table 2, table 3 and table 4.
The physico-chemical analysis result of table 1 resin
| Inspection item | Standard | SP-1068 | Koresin | Embodiment 2 | Embodiment 3 |
| Outward appearance | Yellow sheet | Yellow sheet | Yellow sheet | Yellow sheet | Yellow sheet |
| Weight loss on heating % (65 DEG C of * 2h) | ≤0.5 | 0.3 | 0.15 | 0.14 | 0.16 |
| Ash content % | ≤0.5 | 0.2 | 0.21 | 0.22 | 0.22 |
| Softening temperature/DEG C (ring and ball method) | 95 | 136 | 98 | 99 | |
| Methylol % | ≤1 | 0.5 | 0.5 | 0.4 | 0.4 |
| Free phenol % | ≤2 | 1.6 | 1.6 | 1.4 | 1.4 |
Table 1 analytical results shows, every item is up to standard the requirement of product of the present invention and contrast product.
Table 2 little cooperation properties of rubber test-results (by normal refining glue composition and engineering)
Note: blank for not add tackifying resin
Table 2 data can be found out, after adding tackifying resin, the mooney viscosity [ML (1+4) 100 DEG C] of sizing material all has decline in various degree, wherein to add sizing material the biggest drop of product of the present invention.Add the sizing material mooney scorch time shorten of tackifying resin, wherein the impact of SP-1068 and Koresin is comparatively large, and the impact of product of the present invention is less.
Table 3 sizing material autohension test-results (kN/M)
Note: 1. " can not tear open " as bond strength exceedes the intensity of sample itself.2. blank for not add tackifying resin
As can be seen from Table 3, the initial viscosity of adding the sizing material of each tackifying resin is all excellent, is significantly higher than blank sizing material.Sample is after sudden and violent gas test in 24 hours, and the sizing material viscosity adding various tackifying resin is still fairly good.But along with the prolongation of sudden and violent gas time, the autohension of each sample all has decline in various degree.Wherein after 72 hours, add the initial viscosity of autohension close to check sample of the sample of SP-1068 at sudden and violent gas, add the autohension of the sample of Koresin still preferably.The autohension of adding the sample of Koresin at sudden and violent gas after 240 hours starts to decrease, and the sizing material sample adding product of the present invention all can keep good autohension in the variant time period.From hydrothermal aging test-results, blank sizing material is to hydrothermal aging without significant reaction, and the autohension of sizing material is poor; When hydrothermal aging is after 24 hours and hydrothermal aging after 48 hours, the sizing material adding SP-1068 has larger gap with the autohension of the sizing material adding product of the present invention, the autohension of adding the sizing material of product of the present invention is significantly better than the autohension of the sizing material adding SP-1068, and the autohension of adding the sample of Koresin is then basically identical with the autohension of the sizing material adding product of the present invention.The autohension of adding from heat ageing test result after the sizing material thermal ageing of each tackifying resin is all better than the autohension after check sample thermal ageing, and the autohension of adding after the sample thermal ageing of the autohension after the sample thermal ageing of product of the present invention and interpolation Koresin is basically identical, be all slightly better than the autohension after the sample thermal ageing of adding SP-1068.
Power detected result extracted out by table 4 steel wire
Steel wire extracts power out to add the sample of product of the present invention comparatively greatly, and the sample adding product of the present invention comparatively adds steel wire extraction power large more than the 300N and more than 260N respectively of the sample of SP-1068 and the sample of interpolation Koresin, and effect is very remarkable.
Claims (4)
1. the Alkyl phenolic resin rubber tackifier improved, is characterized in that in the molecular structure of these tackifier containing benzothiazole heterocyclic group.
2. Alkyl phenolic resin rubber tackifier according to claim 1, the benzothiazole heterocyclic group that it is characterized in that in its molecular structure is that the benzothiazole heterogeneous ring compound and alkylphenol by having etherified response function group carries out etherification reaction and form ehter bond and access in molecular structure.
3. Alkyl phenolic resin rubber tackifier according to claim 2, is characterized in that the mol ratio of the benzothiazole heterogeneous ring compound monomer and alkylphenol monomer with etherified response function group synthesizing this resin is 0.001-1: 1.
4. alkyl phenolic resin tackifier according to claim 2, is characterized in that the softening point range of these alkyl phenolic resin tackifier is 85-140 DEG C.
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| CN104974321B (en) * | 2014-04-14 | 2017-07-07 | 江苏国立化工科技有限公司 | A kind of methyl-etherified melamine resin and preparation method thereof |
| CN106608956B (en) * | 2015-10-21 | 2018-11-09 | 华奇（中国）化工有限公司 | A kind of preparation method and application of alkyl phenol-phenol-formaldehyde resin |
| BE1023496B1 (en) * | 2016-03-09 | 2017-04-07 | Sumitomo Bakelite Europe N.V. | Process for the preparation of NOVOLAK ALKYLPHENOL RESINS |
| CN107722204B (en) * | 2017-10-30 | 2020-02-07 | 山东阳谷华泰化工股份有限公司 | Synthesis method of tackifying alkyl phenolic resin |
| CN108192060A (en) * | 2017-12-22 | 2018-06-22 | 江苏国立化工科技有限公司 | Multicomponent is modified green syt high-performance rubber adhesive and preparation method thereof |
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| CN101338028A (en) * | 2007-09-21 | 2009-01-07 | 江苏国立化工科技有限公司 | Method for preparing resorcinol resins |
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| CN101338028A (en) * | 2007-09-21 | 2009-01-07 | 江苏国立化工科技有限公司 | Method for preparing resorcinol resins |
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Denomination of invention: A kind of alkyl phenolic resin rubber tackifier and preparation method Effective date of registration: 20220915 Granted publication date: 20150513 Pledgee: Jiangsu Yixing Rural Commercial Bank Co.,Ltd. Pledgor: JIANGSU GUOLI CHEMICAL TECHNOLOGY Co.,Ltd. Registration number: Y2022980015352 |