CN105622874B - With rosin or the phenol-formaldehyde resin and its preparation method and application of maleic rosin and modified by cardanol - Google Patents
With rosin or the phenol-formaldehyde resin and its preparation method and application of maleic rosin and modified by cardanol Download PDFInfo
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Abstract
The present invention relates to a kind of phenol formaldehyde resins and preparation method thereof, it is modified with rosin or maleic rosin with anacardol, first by phenol, either alkylation reaction or esterification occur in acid condition for maleic rosin with rosin, then the modified phenol formaldehyde resin is obtained by the reaction with formaldehyde in acid condition with anacardol, its softening point is at 80 130 DEG C, with the performance for improving rubbery intensity and tearing toughness, it can be used for adding in rubber size, improve the intensity and tearing toughness of rubber.
Description
Technical field
The present invention relates to one kind being used for phenolic resin varinish, and in particular to a kind of rosin or maleic rosin and anacardol
Modified phenol-formaldehyde resin and its preparation method and application.
Background technology
Rosin is a kind of natural products from pine tree, and structural formula is shown in shown in formula (VIII), contain in rosin there are two
Chemical reaction center：Double bond and carboxyl；By the reaction of double bond or carboxyl, rosin is subjected to the reactions such as addition, esterification, to
Realize the modification for rosin.Wherein maleic rosin is exactly to be obtained by the D-A addition reactions of rosin and maleic anhydride.
Anacardol is also a kind of natural products as rosin, mainly passes through distillation and rectifying by cashew nut shell oil
Product afterwards.Anacardol is a kind of mixture, shown in structure formula (IX), wherein based on cashew nut single phenol, in same anacardol
It containing two phenyl ring, double bond active sites, can react with phenolic resin, while contain longer alkyl chain in anacardol, with
Rubber has preferable compatibility, and the phenolic resin crossed by modified by cardanol can carry out compatible, raising phenol with rubber well
The dispersibility of urea formaldehyde.
Currently, more for the modification of phenolic resin using rosin or anacardol, patent US2532374 discloses cashew nut
Oil modified phenolic resin, patent CN201310007218.5 also disclose a kind of tall oil modified alkyd resin method, that is, use
Toll oil rosin and ready denier oil acid compound replace tall oil.The modified phenol formaldehyde resin of preparation is mostly used in rubber tyre
In triangle rubber part, to promote the intensity of rubber, the rarely seen tyre surface for rubber tyre.
About in application of the resin in rubber tyre, as used vinylite in Michelin patent CN 102869522A
Improve the processing of tyre surface and the performance of wetland earth-grasping force for tyre surface, in same Michelin's patent CN 101636284A
Petropols are added in rubber tread, improve the mechanical property of tyre surface；For tyre surface disclosed in patent CN 102549026A
Phenol-aromatic-terpene resin；Patent CN 103319672A utilize lignin modification phenolic resin for tire with
And a kind of phenol-DCPD resins for tyre surface disclosed in patent CN 103665331A.Proposed by the present invention is mainly to utilize pine
Fragrant or rosin derivative and anacardol are modified phenolic resin, be mainly used for rubber tread to promote rubber tread
Tear resistance and mechanical property.
Invention content
The present invention relates to a kind of phenol-formaldehyde resin of modification, which has raising rubbery intensity and tear-proof strong
The performance of degree.The resin of the modification using phenol, formaldehyde, rosin or maleic rosin and anacardol be modified preparation and
At.
The present invention proposes a kind of phenol-formaldehyde resin of modification, that is, with rosin or maleic rosin and modified by cardanol
Phenol-formaldehyde resin, with following formula (I), formula (II), formula (III) structure it is one or more；
Wherein, R is structure shown in following formula (IV)：
The present invention proposes a kind of preparation method with rosin or the phenol-formaldehyde resin of maleic rosin and modified by cardanol,
First, phenol and rosin or maleic rosin carry out reacting for alkanisation or esterification, then, under the action of catalyst, with anacardol,
The phenol-formaldehyde resin with rosin or maleic rosin and modified by cardanol is obtained by the reaction in formaldehyde；Its reaction equation such as formula (V),
(VI) or shown in (VII)：
Wherein, the R is structure shown in formula (IV)；The R ' is the rosin after alkanisation；The R " is the pine after esterification
It is fragrant；The R " ' is maleic rosin；
In the present invention, first either addition or esterification occur phenol in acid condition for maleic rosin with rosin, so
Modified phenol-formaldehyde resin, the phenol-formaldehyde tree of the modification is obtained by the reaction with formaldehyde in acid condition with anacardol afterwards
The softening point of fat is at 80-130 DEG C.
In preparation method of the present invention, the dosage of the phenol is 60-100 parts, and the dosage of the rosin or maleic rosin is
15-60 parts, the dosage of the anacardol is 40-80 parts, and the dosage of the formaldehyde is 30-80 parts, and the dosage of the catalyst is
0.1-5 parts.The formaldehyde includes 37% formalin.
Preferably, 70-100 parts of the dosage of the phenol, 40-80 parts of the dosage of the formaldehyde, the rosin or Malaysia
Rosin dosage is 45-60 parts, and the dosage of the anacardol is 50-70 parts, and the dosage of the catalyst is 1-3 parts.The formaldehyde
Including 37% formalin.
In preparation method of the present invention, raw material and reagent include：Phenol, formaldehyde (such as 37% formalin), rosin or
Maleic rosin, anacardol, catalyst.
In preparation method of the present invention, the rosin is one or more of Starex, gum rosin or wood rosin
Combination, acid value 130-180, iodine number 150-220.The maleic rosin is the addition compound product of rosin and maleic anhydride,
Its acid value is 130-180, iodine number 110-170.The anacardol is that a kind of aldehydes matter with unsaturated chain carries ten
The aldehydes matter of the alkyl chain of five carbon, iodine number 130-220, preferably iodine number are 150-200.The catalyst is selected from grass
Acid, phosphoric acid, sulfuric acid, p-methyl benzenesulfonic acid, dodecyl benzene sulfonic acid (DBSA), p-hydroxybenzenyl sulfonate any one or it is two kinds arbitrary
Above combination.
Preparation method proposed by the present invention with rosin or the phenol-formaldehyde resin of maleic rosin and modified by cardanol,
In one specific embodiment, the rosin or maleic rosin are reacted into 60-30min at 120-180 DEG C with phenol, are cooled to
90 DEG C, the catalyst and anacardol are added, and the formalin is gradually added dropwise, is gradually warming up to after being added dropwise
160-200 DEG C, vacuum dehydration 30min obtains the phenol-formaldehyde resin of the modification.
In the present invention, the catalyst used is acid catalyst, wherein is divided since oxalic acid (is more than 160 DEG C) at high temperature
Solution, so when using oxalic acid as catalyst, does not use terminator at carbon dioxide and water.Using urging in addition to oxalic acid
When agent, need to be terminated using terminator excessive to prevent reaction from carrying out.Typically, for organic acid such as DBSA, to first
Base benzene sulfonic acid catalyst selects organic bases terminator, then uses inorganic base as eventually the inorganic acids such as sulfuric acid catalyst
Only agent.The terminator is selected from sodium hydroxide, potassium hydroxide, triethanolamine, 1,8- diazabicylos (5,4,0) endecatylene -7
Any one or combinations thereof.The dosage of the terminator is 1-5 parts.Preferably, the terminator is 1-3 parts.
The invention also provides a kind of with the phenol-formaldehyde resin of rosin or maleic rosin and modified by cardanol in rubber tyre
As the application of reinforcing material in face, wherein described with rosin or the phenol-formaldehyde resin packet of maleic rosin and modified by cardanol
Include with formula (I), formula (II), formula (III) structure it is one or more.Present invention rosin or maleic rosin and modified by cardanol
Phenol-formaldehyde resin, there is the performance for improving rubbery intensity and tearing toughness, can be used for adding in rubber size,
The intensity and tearing toughness for improving rubber, promote the tear resistance and mechanical property of rubber tread.
Specific implementation mode
In conjunction with following specific examples, the present invention is described in further detail, and of the invention protects content not limit to
In following embodiment.Without departing from the spirit and scope of the invention, those skilled in the art it is conceivable that variation and excellent
Point is all included in the present invention, and using appended claims as protection domain.Implement the present invention process, condition,
Reagent, experimental method etc. are among the general principles and common general knowledge in the art, this hair in addition to the following content specially referred to
It is bright that content is not particularly limited.
Related art can refer to：Tianrui and Li Yonghong is appointed to write《Rosin chemistry and application》Middle P69-P72 pages,
Rosin and the addition of phenolic resin and esterification and maleic rosin react；Nanjing forest product industry institute writes《It
Right resin manufacturing processes》Middle P240-P241, rosin are reacted with phenolic resin；Yang Donghai compilings《The reprocessing of rosin and
It utilizes》Middle P80-P82, rosin are reacted with phenolic resin；The cashew nut shell oil that United States Patent (USP) US2203206 is introduced, acid or alkali
In the presence of property catalyst, with phenol, resorcinol, methylphenol and other phenols hybrid reactions；Deng.
Embodiment 1
In the four-hole boiling flask of 1L, puts into 1000 parts of phenol and 400 parts of rosin, 1.5 parts of dodecyl benzene sulfonic acid are heated to
160 DEG C, after back flow reaction 60min, after rosin and phenol are reacted, it is cooled to 90 DEG C.Put into 600 parts of anacardol, oxalic acid
30 parts, and 600 parts of formalins are added dropwise in 30min, there are heat release and foam to generate in reaction process, after being added dropwise, body
It is that muddy brown breast body is become from transparent brown liquid；In order to which formaldehyde and phenol and anacardol etc. react abundant, return
Stream reaction 30min, distillation is warming up to 170 DEG C, and to steam the moisture in system, brownish red transparency liquid is presented in system at this time, after
Continuous vacuum dehydration 30min is poured out system with removing remaining moisture and partly free phenol, and rosthornite is obtained after cooling
2023 parts of modified phenol-formaldehyde resins, with formula (I), formula (II), formula (III) structure it is one or more.The modification
Phenol-formaldehyde resin softening point be 90.3 DEG C.The iodine number of experiment anacardol used is 180.
Embodiment 2
Rosin in embodiment 1 is changed to the maleic rosin of equivalent, remaining is the same as embodiment 1.Finally obtain rosthornite
2019 parts, 110.5 DEG C of resin softening point.The iodine number of experiment anacardol used is 180.
Embodiment 3- embodiments 7
Embodiment 3 reduces consumption of oxalic acid, and 200 parts of 200 parts of rosin and maleic rosin is used in combination.Embodiment 4 and embodiment 5 are distinguished
Change the formaldehyde dosage in experiment.Embodiment 6 increases the ratio of rosin or maleic rosin in system respectively with embodiment 7.
Embodiment 8
In the four-hole boiling flask of 1L, 1000 parts of phenol of input and 400 parts of rosin, 1.5 parts of DBSA (dodecyl benzene sulfonic acid),
It is heated to 160 DEG C, after back flow reaction 60min, after rosin and phenol are reacted, is cooled to 90 DEG C.Put into anacardol 600
Part, DBSA8.5 part, and in 30min dropwise addition 600 parts of formalins, reaction process heat release is violent, after being added dropwise, system by
Transparent brown liquid becomes muddy brown breast body；In order to make formaldehyde and phenol and anacardol etc. react abundant, reflux is anti-
30min is answered, distillation is warming up to 170 DEG C, and to steam the moisture in system, brownish red transparency liquid is presented in system at this time, continues true
Sky dehydration 30min, is added DBU4 parts of terminator, stirs 10min, system is poured out, and 2021 parts of trees of rosthornite are obtained after cooling
The softening point of fat, the phenol-formaldehyde resin of the modification is 93 DEG C.The iodine number of experiment anacardol used is 180.
Embodiment 9-10
Implementation steps replace with the concentrated sulfuric acid (embodiment 9) and p-methyl benzenesulfonic acid respectively with embodiment 8, by DBSA therein
(embodiment 10) uses sodium hydroxide (embodiment 9) and triethanolamine (embodiment 10) to be used as terminator accordingly, catalyst with
And terminate the ratio that uses and final product number is shown in Table shown in -1.
Embodiment 11
It is 130 with acid value, the rosin that iodine number is 150 replaces rosin used in embodiment 1, the same embodiment of remaining implementation steps
1, finally obtain 2017 parts of resin, 91 DEG C of resin softening point.
Embodiment 12
It is 180 with acid value, the rosin that iodine number is 220 replaces rosin used in embodiment 1, the same embodiment of remaining implementation steps
1, finally obtain 2018 parts of resin, 102 DEG C of resin softening point.
Embodiment 13
It is anacardol used in 150 anacardol alternative embodiment 1 with iodine number, remaining implementation steps is with embodiment 1, finally
Obtain 2021 parts of resin, 87 DEG C of resin softening point.
Embodiment 14
It is anacardol used in 200 anacardol alternative embodiment 1 with iodine number, remaining implementation steps is with embodiment 1, finally
Obtain 2020 parts of resin, 98 DEG C of resin softening point.
Embodiment 15
The reaction temperature of phenol and rosin is adjusted to 120 DEG C, reaction time 60min by formula with embodiment 1.Back flow reaction
After, 160 DEG C, vacuum dehydration 30min are warming up to, 2018 parts of resin, 91 DEG C of resin softening point are obtained.
Embodiment 16
The reaction temperature of phenol and rosin is adjusted to 180 DEG C, reaction time 60min by formula with embodiment 1.Back flow reaction
After, 200 DEG C, vacuum dehydration 30min are warming up to, 2019 parts of resin, 95 DEG C of resin softening point are obtained.
Embodiment 1-16 can prepare the modified phenol-formaldehyde resin of the present invention.In order to test the resin in sizing material
Application performance, choose the test that the resin that embodiment 1 and embodiment 2 are prepared carries out application performance, 30% stress
Surely stretch, stretch breaking strength, elongation rate of tensile failure according to GB/T 528-2009 methods measure, time of scorch Ts3 is according to GB/T 1233-
2008 methods measure, and Mooney viscosity ML (1+4) is measured according to GB/T 1232.1-2000 methods, tear resistance is according to GB/T
3512-2001 is measured.Contrast sample selects commercially available SL-1081 products.The formula table of sample is shown in Table shown in -2.It is final to survey
Examination the results are shown in Table shown in -3 and table -4.
The sample rosin that present invention rosin or maleic rosin are modified it can be seen from the data of table -3 and table -4
Or the mechanical property of the phenol-formaldehyde resin of maleic rosin and modified by cardanol, tear resistance and incipient scorch curability are equal
Better than reference sample.
Table -2
| Raw material | Modified phenol-formaldehyde resin | Contrast sample 1 | Contrast sample 2 |
| NR | 100 | 100 | 100 |
| N234 | 45 | 45 | 45 |
| VN3 | 7 | 7 | 7 |
| SA | 1.5 | 1.5 | 1.5 |
| ZNO | 3 | 3 | 3 |
| Embodiment 1 | 4 | 0 | 0 |
| Embodiment 2 | 0 | 4 | 0 |
| SP1801 | 0 | 0 | 4 |
| RD | 1 | 1 | 1 |
| 4020 | 1 | 1 | 1 |
| OK1987 | 1 | 1 | 1 |
| S | 2 | 2 | 2 |
| NS | 0.75 | 0.75 | 0.75 |
Table -3
Table -4
| Detection project | SP1801 | Embodiment 1 | Embodiment 2 |
| Aging 72h tearing strengths (N/mm) | 30 | 34 | 36 |
Claims (10)
1. a kind of use the phenol-formaldehyde resin of rosin or maleic rosin and modified by cardanol in rubber tread as reinforcing material
Application, which is characterized in that the phenol-formaldehyde resin have formula (I), formula (II), formula (III) structure it is one or more；
Wherein, R is structure shown in following formula (IV)：
Wherein, its iodine number of the rosin is between 150-220；
Its iodine number of the maleic rosin is between 110-170；
Its iodine number of the anacardol is between 130-220.
2. application as described in claim 1, which is characterized in that the softening point of the phenol-formaldehyde resin is 80-130 DEG C.
3. a kind of preparation method with rosin or the phenol-formaldehyde resin of maleic rosin and modified by cardanol, which is characterized in that first
First, phenol and rosin or maleic rosin progress alkanisation or esterification is reacted, then, under the action of catalyst, with anacardol, first
Aldehyde reaction obtains the phenol-formaldehyde resin with rosin or maleic rosin and modified by cardanol；The reaction equation of the method is such as
Shown in formula (V), (VI) or (VII)：
Wherein, the R is structure shown in formula (IV)；
4. preparation method as claimed in claim 3, which is characterized in that in the method, the dosage of the phenol is 60-100
Part, the dosage of the rosin or maleic rosin is 15-60 parts, and the dosage of the anacardol is 40-80 parts, the dosage of the formaldehyde
It it is 30-80 parts, the dosage of the catalyst is 0.1-5 parts.
5. preparation method as claimed in claim 3, which is characterized in that in the method, the rosin is Starex, fat pine
The combination of one or more of fragrant or wood rosin, acid value is between 130-180, and iodine number is between 150-220.
6. preparation method as claimed in claim 3, which is characterized in that in the method, the maleic rosin is rosin and horse
Carry out the addition compound product of acid anhydrides, acid value is in 130-180, and iodine number is in 110-170；The anacardol is the alkyl with 15 carbon
The aldehydes matter of chain, iodine number is in 130-220.
7. preparation method as claimed in claim 3, which is characterized in that in the method, the catalyst is selected from oxalic acid, phosphorus
Any one or any two or more combinations of acid, sulfuric acid, p-methyl benzenesulfonic acid, dodecyl benzene sulfonic acid, p-hydroxybenzenyl sulfonate.
8. preparation method as claimed in claim 3, which is characterized in that in the method, when the catalyst be except oxalic acid it
When outer catalyst, reaction need to be terminated with terminator, wherein the terminator is sodium hydroxide, potassium hydroxide, three ethyl alcohol
Any one of amine, 1,8- diazabicylos (5,4,0) endecatylene -7 or combinations thereof；The dosage of the terminator is 1-5 parts.
9. preparation method as claimed in claim 3, which is characterized in that by rosin or maleic rosin with phenol at 120-180 DEG C
Lower reaction 60-30min, is cooled to 90 DEG C, adds catalyst and anacardol, and formalin is gradually added dropwise, is added dropwise
It is gradually warming up to 160-200 DEG C, vacuum dehydration 30min afterwards, obtains described with rosin or the benzene of maleic rosin and modified by cardanol
Resinox.
10. application as described in claim 1, which is characterized in that described with rosin or the benzene of maleic rosin and modified by cardanol
Application of the resinox in rubber tread as tearing toughness material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106750069A (en) * | 2016-12-22 | 2017-05-31 | 沈阳化工大学 | A kind of 2,5 thiophene dicarboxylic acid's phenolic foam resins and preparation method thereof |
| CN112442157B (en) * | 2019-09-05 | 2022-09-20 | 彤程化学（中国）有限公司 | Epoxy resin and rosin modified alkylphenol-formaldehyde resin and preparation method and application thereof |
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| US4421891A (en) * | 1978-10-18 | 1983-12-20 | Bridgestone Tire Company Limited | Bead filler rubber composition |
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| US20040181026A1 (en) * | 2003-03-10 | 2004-09-16 | Harima Chemicals, Inc. | Rosin modified phenolic resin, gel varnish using the same, printing ink, printing method, and method for producing rosin modified phenolic resin |
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| TW201410748A (en) * | 2012-09-13 | 2014-03-16 | Dic Graphics Corp | Rosin-modified phenolic resin, ink varnish composition, and print ink |
| CN104130362A (en) * | 2014-07-30 | 2014-11-05 | 广西众昌树脂有限公司 | Preparation method of rosin modified phenolic resin |
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2014
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4421891A (en) * | 1978-10-18 | 1983-12-20 | Bridgestone Tire Company Limited | Bead filler rubber composition |
| GB2186881A (en) * | 1986-02-21 | 1987-08-26 | Westvaco Corp | Modified rosin ester preparation |
| US20040181026A1 (en) * | 2003-03-10 | 2004-09-16 | Harima Chemicals, Inc. | Rosin modified phenolic resin, gel varnish using the same, printing ink, printing method, and method for producing rosin modified phenolic resin |
| CN101045840A (en) * | 2006-03-31 | 2007-10-03 | 住友橡胶工业株式会社 | Rubber composition for coating cord |
| TW201410748A (en) * | 2012-09-13 | 2014-03-16 | Dic Graphics Corp | Rosin-modified phenolic resin, ink varnish composition, and print ink |
| CN103159905A (en) * | 2012-12-21 | 2013-06-19 | 上海美东生物材料有限公司 | Hydrogenated cardanol modified rosin phenolic resin and prepared method thereof |
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