CN105622873A - Modified phenolic reinforcing resin, preparation method thereof, and rubber composition containing resin - Google Patents
Modified phenolic reinforcing resin, preparation method thereof, and rubber composition containing resin Download PDFInfo
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- CN105622873A CN105622873A CN201410697211.5A CN201410697211A CN105622873A CN 105622873 A CN105622873 A CN 105622873A CN 201410697211 A CN201410697211 A CN 201410697211A CN 105622873 A CN105622873 A CN 105622873A
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Abstract
The invention discloses a modified phenolic reinforcing resin and a preparation method thereof. The method comprises the following steps: phenol reacts with formaldehyde in the presence of an acidic catalyst, and carboxylic acid and cashew nut oil are added to modify in order to obtain the modified phenolic reinforcing resin. The invention also discloses a rubber composition containing the modified phenolic reinforcing resin, and an application of the modified phenolic reinforcing resin in improvement of physical and mechanical performances of rubber compounds and prolongation of the scorch time of the rubber compounds. The modified phenolic reinforced resin has the advantages of good reinforcing effect, prolongation of the scorch time, good safety of a rubber compound processing technology, and wide application prospect.
Description
Technical field
The present invention relates to field of rubber technology, be specifically related to a kind of modified phenolic reinforced resin and preparation method thereof and the rubber composition containing this modified phenolic reinforced resin.
Background technology
For in the high sizing material of stretching strength and hardness requirement, such as radial triangle rubber, it is usually added into a certain amount of modified phenolic reinforced resin and methylene donor, at high temperature during sulfuration, methylene donor hexamethylenetetramine or the cross-linking modified reinforcing phenolic resin of hexamethoxy methyl cyanuramide, form network structure, interact to form IPN cross-linked network with vulcanization crosslinking network, and with white carbon black co-action, increase hardness and the modulus of sizing material, play strengthening action. Modified phenolic reinforced resin has been used for manufacturing the products such as tire, rubber roll, rubber conveyer belt, V-belt, sole.
In current rubber industry field, the reinforcing effect of cashew nut oil modified alkyd resin is good, and the hardness of vulcanite and modulus are high, but time of scorch is short, the process safety of rubber size processing is bad, sees that Luo Mengchun, Hu Kui are in " tire industry " 27 volume the 1st phase records of the 35 to 37th page in 2007. Therefore, it is necessary to cashew nut oil modified reinforcing phenolic resin is improved, extend its time of scorch, improve the processing technique safety of rubber size.
Summary of the invention
Present invention aim at providing a kind of new modified phenolic reinforced resin and preparation method thereof, and comprise the rubber composition of described modified phenolic reinforced resin. Modified phenolic reinforced resin of the present invention is applicable to rubber industry field, has the advantages such as reinforcing effect is good, time of scorch extends, sizing material processing technique safety is good
The present invention proposes a kind of modified phenolic reinforced resin, and described modified phenolic reinforced resin is carboxylic acid and cashew nut oil modified reinforcing phenolic resin, and its softening point (is measured according to ring and ball method) as 80-110 DEG C.
Modified phenolic reinforced resin of the present invention is carboxylic acid and cashew nut oil modified. By adding the modified of carboxyl acid component, extend the time of scorch of rubber size, improve the processing technique safety of rubber size; Simultaneously again because also adding cashew nut oil component modification, it is possible to the advantage that maintenance cashew nut oil modified alkyd resin reinforcing effect is excellent. It addition, the modified synergic effect of two class modifying agent, it is possible to improve the reinforcing effect of resin further. And the cashew nut oil modified reinforcing phenolic resin that existing market uses is only with cashew nut oil modified, there is the defect that time of scorch is short.
The preparation method that the invention allows for a kind of modified phenolic reinforced resin, prepares described modified phenolic reinforced resin with carboxylic acid, cashew nut oil modified alkyd resin. In described method, phenol and formaldehyde react in the presence of acidic, heat temperature raising, add carboxylic acid and cashew nut oil modified, obtain purpose product and described modified phenolic reinforced resin.
Specifically, preparation method of the present invention comprises the following steps:
(1) phenol and acidic catalyst are added in reactor, add formaldehyde back flow reaction, then distill, heat up;
(2) add carboxylic acid, cashew nut oil in 110-160 DEG C, at 110-220 DEG C of modified-reaction, be subsequently adding nertralizer catalyst neutralisation, obtain described modified phenolic reinforced resin.
In the present invention, described acidic catalyst is chosen from the mineral acids such as oxalic acid, sulphuric acid, hydrochloric acid, phosphoric acid, alkyl benzene sulphonate and a kind of, two or more the combination in any of organic acid.
In the present invention, described formaldehyde can select the formalin of concentration 35-52%, paraformaldehyde or metaformaldehyde.
In the present invention, described carboxylic acid is selected from the one in following material, two or more combination in any: the mixture of benzoic acid, oxybenzoic acid, P-hydroxybenzoic acid, p-phthalic acid, phthalic acid, M-phthalic acid, aphthenic acids, fatty acid, Colophonium and fatty acid, tall oil.
In the present invention, described cashew nut oil refers to the cashew nut oil obtained by cashew nut shell liquid through decarboxylation, and its main component is Cardanol.
In the present invention, described nertralizer is chosen from the one in following material, two or more combination in any: inorganic base and the organic bases such as sodium hydroxide, potassium hydroxide, triethanolamine, diethanolamine, triethylamine, tri-n-butylamine, Tri-n-Propylamine, trien, diethylenetriamines, 1,8-diazabicylo 11 carbon-7-alkene.
The invention allows for a kind of modified phenolic reinforced resin obtained by described preparation method. Described modified phenolic reinforced resin is a kind of by carboxylic acid with cashew nut oil modified reinforcing phenolic resin, and its softening point (measures according to ring and ball method) as 80-110 DEG C.
The modified phenolic reinforced resin of the present invention is used as the reinforcing agent of rubber industry, and provides the rubber composition comprising resin of the present invention. This rubber composition can include rubber, phenol-formaldehyde resin modified of the present invention, methylene donor; Possibly together with the compounding ingredient that other rubber industries such as white carbon black, softening agent, age resistor, vulcanizing agent, vulcanizing activator, vulcanization accelerator are conventional. The rubber composition of the present invention can be used to make rubber, for instance tire, rubber conveyer belt etc.
Modified phenolic reinforced resin of the present invention contained in the rubber composition of the present invention is 4-16 part/100 part rubber.
In rubber composition of the present invention, described methylene donor is selected from hexamethylenetetramine, hexamethoxy methyl cyanuramide and their mixture. Methylene donor contained in the rubber composition of the present invention is 0.3-2 part/100 part rubber.
Present invention also offers the application in extending time of scorch of the described modified phenolic reinforced resin. In a specific embodiment, with the addition of the time of scorch of the sizing material of described modified phenolic reinforced resin to be obviously prolonged.
Present invention also offers the application in improving physical and mechanical properties of the described modified phenolic reinforced resin. In a specific embodiment, with the addition of the physical and mechanical propertiess such as the stretching strength of sizing material of described modified phenolic reinforced resin, hot strength, elongation at break all to improve.
Detailed description of the invention
In conjunction with specific examples below, the present invention is described in further detail, and the protected content of the present invention is not limited to following example. Under the spirit and scope without departing substantially from inventive concept, those skilled in the art it is conceivable that change and advantage be all included in the present invention, and with appending claims for protection domain. Implementing the process of the present invention, condition, reagent, experimental technique etc., outside the lower content mentioned specially, be the universal knowledege of this area and known general knowledge, the present invention is not particularly limited content.
The mensuration of softening point, carries out according to National Standard of the People's Republic of China GB/T4507-2014 " asphalt softening point algoscopy ring and ball method ".
Embodiment 1,2,3 and comparative example: the preparation of modified phenolic reinforced resin
Preparation process: adding in reactor by phenol 100 grams, p-methyl benzenesulfonic acid 0.5 gram, stirring is warming up to 90 DEG C, adds 37% formalin 24.5 grams, paraformaldehyde 12 grams, is then refluxed for reaction 1 hour. Distillation, is warming up to 135 DEG C and adds oxalic acid 0.5 gram, LABS 2.5 grams, add modifier A (carboxylic-acid substance, in Table 1), modifying agent B (carboxylic-acid substance, in Table 1), cashew nut oil, be warming up to 200 DEG C of reactions. It is subsequently adding 1.5 grams of triethanolamine to neutralize, obtains modified phenolic reinforced resin, survey softening point. The feeding quantity of each embodiment and comparative example and the softening point of gained modified phenolic reinforced resin are in Table 1.
Table 1
| Embodiment | Modifier A, gram | Modifying agent B, gram | Cashew nut oil, gram | Softening point, DEG C |
| 1 | Colophonium, 40 | Ready denier oil acid, 30 | 40 | 98 |
| 2 | Benzoic acid, 50 | 0 | 50 | 93 |
| 3 | P-phthalic acid, 20 | Oleic acid, 5 | 25 | 86 |
| Comparative example | 0 | 0 | 40 | 96 |
The performance evaluation of embodiment 4 rubber composition and rubber size
Rubber composition (rubber size) formula (mass parts): natural rubber 100.0, white carbon black N37560.0, operation oil 3.4, stearic acid 2.0, zinc oxide 4.0, sulfur 3.0, modified phenolic reinforced resin of the present invention 10 (select respectively embodiment 1,2, the modified phenolic reinforced resin for preparing of comparative example), hexamethylenetetramine 1.0, accelerator N-tertiary butyl-2-[4-morpholinodithio sulfenamide 2.0, age resistor 2,2,4-trimethyl-1,2-dihyaroquinoline polymer 1.5, protection wax 1.0.
The mensuration of time of scorch, carries out according to National Standard of the People's Republic of China GB/T1233-2008 " the mensuration disk of half finished rubber incipient cure characteristic is sheared viscosimeter and is measured ". The mensuration of the physical and mechanical propertiess such as stretching strength, carries out according to National Standard of the People's Republic of China GB/T528-2009 " mensuration of vulcanite or thermoplastic elastomer tensile stress-strain performance ". Measurement result is table 2 such as.
Table 2
As seen from Table 2, compared with the sizing material being added with comparative example resin, the time of scorch of the sizing material being added with embodiment 1 modified phenolic reinforced resin and the sizing material that is added with embodiment 2 modified phenolic reinforced resin is obviously prolonged. From physical and mechanical propertiess such as hot strengths, it is added with the sizing material of embodiment 1 resin and embodiment 2 resin also superior to comparative example. Test result indicate that, the time of scorch of the rubber composition adding modified phenolic reinforced resin of the present invention is obviously prolonged, the safety adding man-hour at rubber size is better, its physical and mechanical properties includes stretching strength, hot strength, elongation at break etc. and also significantly improves, and is conducive to improving the quality of the rubbers such as tire.
Claims (10)
1. a modified phenolic reinforced resin, it is characterised in that described modified phenolic reinforced resin is carboxylic acid and cashew nut oil modified reinforcing phenolic resin, measures its softening point according to ring and ball method and is 80-110 DEG C.
2. the preparation method of a modified phenolic reinforced resin, it is characterised in that phenol and formaldehyde react in the presence of acidic, heat temperature raising, adds carboxylic acid and cashew nut oil modified, obtains modified phenolic reinforced resin as claimed in claim 1.
3. preparation method as claimed in claim 2, it is characterised in that comprise the following steps:
(1) phenol and acidic catalyst are added in reactor, add formaldehyde back flow reaction, then distill, heat up;
(2) add carboxylic acid, cashew nut oil in 110-160 DEG C, at 110-220 DEG C of modified-reaction, be subsequently adding in nertralizer and described acidic catalyst, obtain described modified phenolic reinforced resin.
4. preparation method as claimed in claim 2, it is characterized in that, described carboxylic acid is any one or combination in any in the mixture of benzoic acid, oxybenzoic acid, P-hydroxybenzoic acid, p-phthalic acid, phthalic acid, M-phthalic acid, fatty acid, fatty acid and Colophonium, tall oil, aphthenic acids.
5. preparation method as claimed in claim 2, it is characterised in that the mass ratio of described carboxylic acid and phenol is 0.1-0.7: 1.
6. preparation method as claimed in claim 2, it is characterised in that the mass ratio of described cashew nut oil and phenol is 0.1-0.6: 1.
7. a rubber composition, it is characterised in that it contains rubber and modified phenolic reinforced resin as claimed in claim 1.
8. rubber composition as claimed in claim 7, it is characterised in that the content of described modified phenolic reinforced resin is 4-16 part/100 part rubber.
9. rubber composition as claimed in claim 7, it is characterised in that contain methylene donor further; The content of described methylene donor is 0.3-2 part methylene donor/100 part rubber.
10. modified phenolic reinforced resin as claimed in claim 1 is extending sizing material time of scorch, the application strengthened in compound physical mechanical performance.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107118317A (en) * | 2017-06-09 | 2017-09-01 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of Cardanol Modified PF Resin |
| CN112778580A (en) * | 2020-12-28 | 2021-05-11 | 贵州轮胎股份有限公司 | All-steel tire nylon cord fabric rubber material and preparation method thereof |
| CN113004476A (en) * | 2019-12-20 | 2021-06-22 | 彤程化学（中国）有限公司 | Phenolic resin with nano-sized structure and preparation and application thereof |
| CN115141332A (en) * | 2022-08-15 | 2022-10-04 | 山东阳谷华泰化工股份有限公司 | Synthetic method of modified phenolic resin and obtained product |
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| CN102177201A (en) * | 2008-08-19 | 2011-09-07 | 株式会社普利司通 | Rubber composition |
| CN102558473A (en) * | 2011-12-28 | 2012-07-11 | 北京彤程创展科技有限公司 | Cashew nut oil-modified phenolic resin and preparation method thereof |
| CN102634081A (en) * | 2012-05-02 | 2012-08-15 | 三角轮胎股份有限公司 | Anti-aging lower bead filler rubber composition for all steel radial tire |
| CN103910841A (en) * | 2013-01-09 | 2014-07-09 | 华奇（张家港）化工有限公司 | Tall oil modified phenolic resin and preparation method thereof |
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2014
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| US4421891A (en) * | 1978-10-18 | 1983-12-20 | Bridgestone Tire Company Limited | Bead filler rubber composition |
| CN101092473A (en) * | 2007-08-13 | 2007-12-26 | 山东圣泉化工股份有限公司 | Anti hot cracking phenol-formaldehyde resin in use for foundry |
| CN102177201A (en) * | 2008-08-19 | 2011-09-07 | 株式会社普利司通 | Rubber composition |
| CN102558473A (en) * | 2011-12-28 | 2012-07-11 | 北京彤程创展科技有限公司 | Cashew nut oil-modified phenolic resin and preparation method thereof |
| CN102634081A (en) * | 2012-05-02 | 2012-08-15 | 三角轮胎股份有限公司 | Anti-aging lower bead filler rubber composition for all steel radial tire |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107118317A (en) * | 2017-06-09 | 2017-09-01 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of Cardanol Modified PF Resin |
| CN113004476A (en) * | 2019-12-20 | 2021-06-22 | 彤程化学（中国）有限公司 | Phenolic resin with nano-sized structure and preparation and application thereof |
| CN113004476B (en) * | 2019-12-20 | 2023-05-05 | 彤程化学（中国）有限公司 | Phenolic resin with nano-size structure and preparation and application thereof |
| CN112778580A (en) * | 2020-12-28 | 2021-05-11 | 贵州轮胎股份有限公司 | All-steel tire nylon cord fabric rubber material and preparation method thereof |
| CN115141332A (en) * | 2022-08-15 | 2022-10-04 | 山东阳谷华泰化工股份有限公司 | Synthetic method of modified phenolic resin and obtained product |
| CN115141332B (en) * | 2022-08-15 | 2023-09-12 | 山东阳谷华泰化工股份有限公司 | Synthesis method of modified phenolic resin and obtained product |
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Application publication date: 20160601 |