CN105622872B - A kind of cashew nut oil modified novolac resin and its preparation method and application - Google Patents
A kind of cashew nut oil modified novolac resin and its preparation method and application Download PDFInfo
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Abstract
The invention discloses the cashew nut oil modified novolac resins and preparation method thereof for including formula (I), formula (II), under phenol and catalyst existence condition, cashew nut shell oil is added dropwise, cashew nut shell oil is set fully to be reacted with phenol, then coupling agent is added and carries out polycondensation reaction, it is reacted after heating, cashew nut oil modified novolac resin is made.The invention also discloses the purposes that the cashew nut oil modified alkyd resin is used as the reinforcing agent of rubber and tire.The present invention improves raw material availability, and environmental protection increases rubber strength, can be widely applied in rubber tyre industry.
Description
Technical field
The present invention relates to organic high molecular compound, in particular to a kind of cashew nut oil modified novolac resin and its systems
The purposes of Preparation Method and its reinforcing agent as rubber and tire.
Background technology
Cashew nut shell oil is a kind of abundant reproducible natural phenol, belongs to the environmentally protective raw material of industry, and cashew nut shell is passed through
Squeezing obtains cashew nut crude oil (mainly cashew acid), then obtains cashew nut shell oil through high temperature decarboxylation, includes mainly 4 kinds of ingredients：Waist
The oligomer of fruit single phenol, cashew nut diphenol, methyl cashew nut diphenol and anacardol, structural formula are as follows：
Wherein, the value of n can be 1,2 or 3.
The aromatic ring and side chain of cashew nut shell oil all have reactivity, and under the action of catalyst, cashew nut shell oil not only can be with
Formaldehyde reacts, and pendant double bonds can react with phenol.Therefore, cashew nut shell oil can be applied to phenolic resin
In resin is modified.
Exist according to Ke Jin refinings《It is printed when chemical industry》, will be by certain ratio described in the 6th the 26-38 pages of the phase of volume 22 in December, 2008
The cashew nut shell oil and formaldehyde that example calculates are added in reaction kettle, with Ba (OH)2For catalyst, cardanol-aldehyde resin is made.
Phenol first is made using phenol is reacted under the conditions of acidic catalyst with formaldehyde in Chinese patent CN102558473
Then aldehyde polycondensate cashew nut shell oil is added in phenol formaldehyde (PF) condensation polymer, temperature reaction is simultaneously evaporated under reduced pressure, and obtained cashew nut shell oil changes
The phenolic resin of property.
Exist according to He Jinliang etc.《Plastic engineering》, 1989, the 4th phase, described in the 14-16 pages, in inorganic acid or Louis
Under the catalytic action of acid, phenol, which is easily alkylated with the cashew nut shell oil after decarboxylation, to react, and reaction equation is as follows：
United States Patent (USP) US2203206 describes cashew nut shell oil and is directly heating, in the presence of acid or basic catalyst, with benzene
Phenol, resorcinol, methylphenol and the mixing of other phenols, the method for final tree esterification reaction synthetic resin.
A kind of preparation method for cashew nut oil modified alkyd resin that patent CN101081890 is proposed, phenol and cashew nut shell
Oily alkanisation first in the presence of acidic, then plus alkali adjusts pH, adds formaldehyde and obtains thermosetting phenolic resin.
The preparation method of cashew nut oil modified novolac resin of the present invention overcomes the same of prior art preparation
Free-phenol and the free higher problem of anacardol content, improve raw material availability and are conducive to environmental protection in resinoid,
Obtained products application is more advantageous to the reinforcing property for improving sizing material in rubber.
Invention content
The present invention provides a kind of cashew nut oil modified alkyd resins, and it includes chemical constitution formula (I)s and formula (II)：
Wherein, the value of n can be 1,2 or 3；The integer that the value of X is 1~120.
The present invention also provides a kind of preparation methods of cashew nut oil modified alkyd resin, and the method includes walking as follows
Suddenly：
(1) phenol, acidic catalyst are added in reactor, cashew nut shell oil, controlling reaction temperature 80 DEG C~140 is added dropwise
DEG C, so that phenol is reacted with cashew nut shell oil；
(2) and then coupling agent is added, controlling reaction temperature makes phenol react 1 hour with formaldehyde, so at 90 DEG C~110 DEG C
It heats up afterwards and steams the water that reaction generates；
(3) between mixed liquor obtained by abovementioned steps (2) being warming up to 150 DEG C~220 DEG C, reaction 1~5 hour is kept, so
Afterwards in vacuum degree -0.03MPa~-0.1MPa vacuum distillation, until the softening point of resin is at 70 DEG C~120 DEG C, in neutralizer
And catalyst, obtain cashew nut oil modified novolac resin；Wherein, the cashew nut oil modified novolac resin includes following formula
(I) and formula (II) structure.
Wherein, comprising such as following formula (1)~formula (11) structure in the mixed liquor that step (1) reaction generates：
Wherein, the cashew nut shell oil is cashew nut single phenol, cashew nut diphenol or both mixing.Cashew nut shell oil can be cashew nut list
Phenol can also be the mixture of cashew nut diphenol or both, and the cashew nut shell oil of two double bonds, the benzene that can be reacted are contained for alkyl chain
Phenol quantity is 1 or 2, and the cashew nut shell oil of three double bonds is contained for alkyl chain, and the phenol quantity that can be reacted is 1,2 or 3, and phenol connects
The position entered is contraposition or the ortho position of phenolic hydroxyl group.
Wherein, the catalyst is one kind or its group in p-methyl benzenesulfonic acid, alkyl benzene sulphonate, oxalic acid, hydrochloric acid and sulfuric acid
It closes, mole dosage is the 0.2%~1.5% of phenol mole dosage.
Wherein, the cashew nut shell oil is the C15 polyphenol that side chain contains unsaturated double-bond, and the mole dosage of cashew nut oil is benzene
The 3%~20% of phenol mole dosage.
Wherein, the feed postition of the cashew nut shell oil is to be added dropwise, and time control is added in 0.1~1h, temperature is controlled 80
DEG C~140 DEG C, the reaction time is 0.1~3 hour.
Wherein, the coupling agent is the formalin and one or both of paraformaldehyde that mass fraction is 37%
The molar ratio of mixing, coupling agent and phenol is 0.5~0.76:1.
Wherein, after coupling agent formaldehyde reaction 1h is added and steams the water that reaction generates, the reaction temperature of system is upgraded to 150 DEG C
~220 DEG C, the reaction time is 1~5 hour.
Wherein, the neutralizer is sodium hydroxide, potassium hydroxide, ammonium hydroxide, alkylamine, triethanolamine, diethanol amine, diethyl
Amine, triethylamine, aniline, triethylene tetramine, 1,8- diazabicylos-bicyclic (5,4,0) -7- hendecenes (DBU), divinyl three
One kind or combinations thereof in amine, tetraethylenepentamine, hexamethylenetetramine.
The principle that preparation method of the present invention is related to includes：
The first step：Under the catalytic action of acidic catalyst, the double bond of cashew nut shell oil side chain is opened occurs alkanisation with phenol
Reaction generates cashew nut shell oil-phenol oligomer.
Second step：Phenol, cashew nut shell oil-phenol oligomer occur condensation reaction with formaldehyde and generate cashew nut oil modified phenol
Urea formaldehyde.
Wherein, the value of n can be 1,2 or 3；The integer that the value of X is 1~120.
The preparation method of thermoplasticity cashew nut oil modified alkyd resin of the present invention, first in phenol and catalyst existence condition
Under, cashew nut shell oil is added dropwise, cashew nut shell oil is made fully to be reacted with phenol, generates alkylated product, then formaldehyde is added to carry out polycondensation reaction, system
Obtain resin.It is prepared compared with the method for resin with first obtained phenol formaldehyde (PF) condensation polymer in the prior art and then by cashew nut shell oil,
Preparation method of the present invention can make cashew nut shell oil reaction abundant, reduce the anacardol and phenol content to dissociate in resin, be conducive to
Environmental protection, obtained products application are more advantageous to the reinforcing property for improving sizing material in rubber.
The present invention also provides a kind of applications of cashew nut oil modified alkyd resin, will the waist comprising formula (I), formula (II)
Shell oil modified phenolic resin is used as the reinforcing agent of rubber and tire.When in use, need 5%~15% mass parts of cooperation six sub-
Tetramine (HMT) carries out crosslinking curing, plays strengthening action.
In preparation method of the present invention, due to cashew nut shell oil elder generation and phenol reactant, the anacardol and benzene that dissociate in final products
Very low (the cashew nut single phenol of phenol content<0.5%, cashew nut diphenol<0.1%, phenol<1%) raw material availability, is not only increased, and
Environmental protection is applied to rubber and tyre industry, plays a part of to increase rubber strength.
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.
The cashew nut oil modified phenolic resin that following embodiment is prepared, mainly by such as formula (I) and formula (II) institute
The compound composition shown.
Wherein, the value of n can be 1,2 or 3；The integer that the value of X is 1~120.
Formula (I) and formula (II) chemical combination in the phenolic resin cashew nut oil modified about obtained product produced according to the present invention
The determination of object is owned for those skilled in the art according to what chemical principle of the present invention and existing literature report can determine
Compound.
In reaction process of the present invention, with cashew nut shell oil alkylation reaction first occurs for phenol in the presence of acidic, obtains
Formula (1)~formula (11) structural compounds；
Then plus coupling agent (37% formalin, paraformaldehyde) reaction, according to its reaction principle, (reaction is happened at
The ortho para position of phenolic hydroxyl group) it can determine, what the method for the present invention and following embodiment were prepared is by such as formula (I) and formula
(II) the cashew nut oil modified phenolic resin of compound represented composition.
Related art content can refer to following：
He Jinliang etc. exists《Plastic engineering》, 1989, the 4th phase, described in the 14-16 pages, in inorganic acid or lewis acid
Catalytic action under, phenol, which is easily alkylated with the cashew nut shell oil after decarboxylation, to react；
The cashew nut shell oil that United States Patent (USP) US2203206 is introduced is directly heating, in the presence of acid or basic catalyst, with benzene
Phenol, resorcinol, methylphenol and other phenols hybrid reactions；
A kind of preparation method for cashew nut oil modified alkyd resin that patent CN101081890 is proposed, phenol and cashew nut shell
Oily alkanisation first in the presence of acidic etc..
Embodiment 1
In tetra- mouthfuls of round-bottom reaction flasks of 500ml equipped with blender, thermometer, reflux condenser and dropping funel, add
Enter 188g (2mol) phenol, 2.4g p-methyl benzenesulfonic acid and 0.6g oxalic acid, be heated to 100 DEG C, 56g cashew nut shell oils are added dropwise, 10min adds
It is complete, 1h is reacted, 37% formalin 58.4g and paraformaldehyde 14.4g is then added, flows back after 30min, heats up and steam
The water generated is reacted, is warming up to 160 DEG C, then -0.10MPa is evaporated under reduced pressure, and after removing water and part free-phenol, 2.2g is added
Triethanolamine is neutralized, and cashew nut oil modified phenolic resin is made.The softening point of resin is 75.2 DEG C, free-phenol
0.76%, cashew nut single phenol 0.20% of dissociating, cashew nut diphenol of dissociating 0.05%.
Embodiment 2
In tetra- mouthfuls of round-bottom reaction flasks of 500ml equipped with blender, thermometer, reflux condenser and dropping funel, add
Enter 188g (2mol) phenol, 3.6g p-methyl benzenesulfonic acid is heated to 120 DEG C, and 56g cashew nut shell oils are added dropwise, and 30min is added, and reacts
Then 0.5h is added 37% formalin 77.8g and paraformaldehyde 10.2g, flows back after 30min, heat up and steam reaction
The water of generation is warming up to 180 DEG C, and then -0.08MPa is evaporated under reduced pressure, and after removing water and part free-phenol, 50%NaOH is added
Aqueous solution 1.5g is neutralized, and cashew nut oil modified phenolic resin is made.The softening point of resin is 93.5 DEG C, free-phenol
0.77%, cashew nut single phenol 0.20% of dissociating, free cashew nut diphenol is not detected.
Embodiment 3
In tetra- mouthfuls of round-bottom reaction flasks of 500ml equipped with blender, thermometer, reflux condenser and dropping funel, add
Enter 188g (2mol) phenol, 98% concentrated sulfuric acid 0.88g is heated to 120 DEG C, and 82g cashew nut shell oils are added dropwise, and 60min is added, and reacts
Then 0.5h is added 37% formalin 74.6g and paraformaldehyde 16.8g, flows back after 30min, heat up and steam reaction
The water of generation is warming up to 180 DEG C, and then -0.05MPa is evaporated under reduced pressure, after removing water and part free-phenol, with 27% ammonium hydroxide
0.56g is neutralized, and cashew nut oil modified phenolic resin is made.The softening point of resin is 106.7 DEG C, free-phenol
0.62%, cashew nut single phenol 0.03% of dissociating, free cashew nut diphenol is not detected.
Embodiment 4
In tetra- mouthfuls of round-bottom reaction flasks of 500ml equipped with blender, thermometer, reflux condenser and dropping funel, add
Enter 188g (2mol) phenol, dodecyl benzene sulfonic acid 1.9g is heated to 135 DEG C, and 26g cashew nut shell oils are added dropwise, and 20min is added, instead
2h is answered, 37% formalin 77.8g and paraformaldehyde 10.2g is then added, flows back after 30min, heats up and steam reaction
The water of generation is warming up to 210 DEG C, and then -0.03MPa is evaporated under reduced pressure, after removing water and part free-phenol, with DBU 0.91g
It is neutralized, cashew nut oil modified phenolic resin is made.The softening point of resin is 92.1 DEG C, and free-phenol 0.43% dissociates
Cashew nut single phenol 0.08%, free cashew nut diphenol are not detected.
Embodiment 5
In tetra- mouthfuls of round-bottom reaction flasks of 500ml equipped with blender, thermometer, reflux condenser and dropping funel, add
Enter 188g (2mol) phenol and p-methyl benzenesulfonic acid 4.6g, be heated to 90 DEG C, cashew nut shell oil 108g is added dropwise, reacts 3h, be then added
After paraformaldehyde 33.6g, the 30min that flows back, heats up and steam the water that reaction generates, be warming up to 190 DEG C, then -0.1MPa is depressurized
Distillation is neutralized after removing water and part free-phenol with triethylamine 2.7g, and cashew nut oil modified phenolic resin is made.
The softening point of resin is 96.2 DEG C, free-phenol 0.54%, and dissociate anacardol 0.14%, and free cashew nut diphenol is not detected.
Embodiment 6
In tetra- mouthfuls of round-bottom reaction flasks of 500ml equipped with blender, thermometer, reflux condenser and dropping funel, add
Enter 188g (2mol) phenol, p-methyl benzenesulfonic acid 2.6g and dodecyl benzene sulfonic acid 1.2g, be heated to 110 DEG C, 68g cashew nut shells are added dropwise
Oil, 40min are added, and react 1h, and 37% formalin 77.8g and paraformaldehyde 10.2g is then added, after the 30min that flows back,
It heats up and steams the water that reaction generates, be warming up to 200 DEG C, then -0.1MPa is evaporated under reduced pressure, and removes water and part free-phenol
Afterwards, it is neutralized with 50%KOH aqueous solutions 1.9g, cashew nut oil modified phenolic resin is made.The softening point of resin is 114.6
DEG C, free-phenol 0.41%, dissociate anacardol 0.13%, and free cashew nut diphenol is not detected.
Reinforcing rubber benchmark test
Rubber compounding (mass parts)：Natural rubber 100, carbon black 60, operation oil 3.4, zinc oxide 4, stearic acid 2, sulphur 3,
Anti-aging agent NS2, anti-aging agent RD 1.5, protection wax 1, reinforced resin sample 10, HMT.
Reference experiments
Other cashew nut oil modified alkyd resins of Reference Example 1
In tetra- mouthfuls of round-bottom reaction flasks of 500ml equipped with blender, thermometer, reflux condenser and dropping funel, add
Enter 188g (2mol) phenol 3.6g p-methyl benzenesulfonic acid, is heated to 100 DEG C and 37% formalin 77.8g and more is added in sequence
Polyformaldehyde 10.2g reacts 1h, steams the water that reaction generates, and phenol-formaldehyde condensation polymer is made.Then cashew nut shell oil 56g is added
In phenol-formaldehyde condensation polymer, controlling reaction temperature is 160 DEG C and reacts 2.5 hours, is kept under the conditions of vacuum degree -0.08MPa
Then 15min is neutralized with triethanolamine 3.2g, cashew nut oil modified alkyd resin is made.The softening point of the resin is 92.5
DEG C, free phenol content 2.69%, dissociate anacardol 2.83%, cashew nut diphenol of dissociating 0.79%.
Reinforcing rubber results of property such as the following table 1.
1 reinforcing rubber results of property of table
The cashew nut oil modified phenolic aldehyde formaldehyde resin (embodiment of the present invention is added it can be seen from mechanical performance data in upper table
2) after, the stretching strength of sizing material increases, and breaking strength and elongation at break improve, and hardness increases, and first prepares phenol-formaldehyde
Condensation polymer adds cashew nut shell oil to prepare modified phenolic resin (Reference Example 1) and compares again, it is seen that cashew nut shell prepared by the method for the present invention
Oil modified phenolic resin is more advantageous to the reinforcing property for improving sizing material.Next, the experimental results showed that, waist prepared by the method for the present invention
Shell oil modified phenolic resin has many advantages, such as that rubber unvulcanizate is partially hard, stiffening property is more preferable, is not easy clot, is conducive to improve triangle
The yield rate of glue.Furthermore free-phenol, the free cashew nut contained in cashew nut oil modified alkyd resin prepared by the method for the present invention
Single phenol, free cashew nut diphenol content are lower, more environmentally-friendly.
Claims (6)
1. a kind of preparation method of cashew nut oil modified novolac resin, which is characterized in that described method includes following steps：
(1) phenol, acidic catalyst being added in reactor, cashew nut shell oil is added dropwise, regulation and control reaction temperature is 80 DEG C~140 DEG C,
Phenol is set to be reacted with cashew nut shell oil；Wherein, the feed postition of the cashew nut shell oil is to be added dropwise, and the addition time is 0.1~1h, reaction
Time is 0.1~3 hour；
(2) coupling agent is added in preceding step (1) reaction gained mixed liquor, regulation and control reaction temperature is 90 DEG C~110 DEG C, makes benzene
Phenol reacts 0.1~1 hour with coupling agent, then heats up and steams the water that reaction generates；
(3) mixed liquor obtained by abovementioned steps (2) is warming up to 150 DEG C~220 DEG C, reaction 1~5 hour is kept, then in vacuum
Degree -0.03MPa~-0.1MPa vacuum distillation, until the softening point of resin is 70 DEG C~120 DEG C, with neutralizer catalyst neutralisation,
Obtain cashew nut oil modified novolac resin；Wherein, the acidic catalyst be alkyl benzene sulphonate, oxalic acid, phosphoric acid, hydrochloric acid and
One kind in sulfuric acid or combinations thereof；The mole dosage of the catalyst is the 0.2%~1.5% of phenol mole dosage；In described
It is sodium hydroxide, potassium hydroxide, ammonium hydroxide, alkylamine, triethanolamine, diethanol amine, aniline, triethylene tetramine, 1,8- bis- with agent
One kind or combinations thereof in bicyclic (5,4, the 0) -7- hendecenes (DBU) of azabicyclic -, diethylenetriamine, tetraethylenepentamine；
Wherein, the coupling agent is the mixing of one or both of the formalin of mass fraction 37%, paraformaldehyde.
2. preparation method as described in claim 1, which is characterized in that include in the mixed liquor that step (1) reaction generates
Such as following formula (1)~formula (11) structure：
3. preparation method as described in claim 1, which is characterized in that the cashew nut shell oil be cashew nut single phenol, cashew nut diphenol or
The two mixes.
4. preparation method as described in claim 1, which is characterized in that the cashew nut shell oil is that side chain contains unsaturated double-bond
C15 polyphenol；The mole dosage of the cashew nut shell oil is the 3%~20% of phenol mole dosage.
5. preparation method as described in claim 1, which is characterized in that the molar ratio of the coupling agent and phenol be 0.5~
0.76:1。
6. a kind of cashew nut oil modified novolac resin being prepared by any one the method for Claims 1 to 5.
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| CN106674456B (en) * | 2016-12-30 | 2019-12-13 | 安徽美东生物材料有限公司 | Preparation method of modified phenolic resin |
| CN108250378A (en) * | 2017-12-22 | 2018-07-06 | 江苏国立化工科技有限公司 | Environment-friendly rubber reinforcing agent and preparation method thereof |
| CN108129623A (en) * | 2018-01-03 | 2018-06-08 | 苏州市明大高分子科技材料有限公司 | Cashew nut oil modified phenolic aldehyde acrylic resin, preparation method and application |
| CN108752546A (en) * | 2018-05-17 | 2018-11-06 | 苏州保力瑞生物材料科技开发有限公司 | A kind of plant polyenoid phenol phenol-formaldehyde resin modified and preparation method thereof |
| CN111471227A (en) * | 2020-04-24 | 2020-07-31 | 广东百卓鞋业有限公司 | Anti-electric shock double-density primer and preparation method thereof |
| CN111635592A (en) * | 2020-05-08 | 2020-09-08 | 安徽建筑大学 | Cable composite material for engineering equipment and preparation method and application thereof |
| CN112480497B (en) * | 2020-11-25 | 2022-10-25 | 北京彤程创展科技有限公司 | Composition for preparing rubber material, rubber material and preparation method thereof, and blowout preventer |
| CN113372522B (en) * | 2021-07-30 | 2022-05-24 | 上海菲诺利克新材料科技有限公司 | Modified phenolic resin and preparation method thereof |
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| US2203206A (en) * | 1937-05-14 | 1940-06-04 | Gen Plastics Inc | Resin from cashew nutshell oil and another phenol |
| JP2007246689A (en) * | 2006-03-16 | 2007-09-27 | Sumitomo Bakelite Co Ltd | Phenolic resin composition for friction material, and friction material |
| CN101143917A (en) * | 2006-09-14 | 2008-03-19 | 浙江南方塑胶制造有限公司 | Cashew shell modified alkyd resin and preparation method thereof |
| CN100519610C (en) * | 2007-07-25 | 2009-07-29 | 山东圣泉化工股份有限公司 | Preparation method of cashew nut oil modified alkyd resin |
| US8686071B2 (en) * | 2010-07-01 | 2014-04-01 | The Goodyear Tire & Rubber Company | Rubber composition, preparation and tire with component |
| CN102558473B (en) * | 2011-12-28 | 2016-08-24 | 北京彤程创展科技有限公司 | A kind of cashew nut oil modified alkyd 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 |
| CN103102478B (en) * | 2013-01-21 | 2014-12-10 | 卡德莱化工(珠海)有限公司 | Cashew nut shell oil alkyd resin and preparation method thereof |
| CN103102462A (en) * | 2013-01-21 | 2013-05-15 | 卡德莱化工(珠海)有限公司 | Cashew nut shell oil modified phenolic resin as well as preparation method and application thereof |
| CN103073690B (en) * | 2013-01-21 | 2015-04-29 | 卡德莱化工(珠海)有限公司 | Cashew nut shell oil-modified phenolic resin as well as preparation method and application thereof |
| CN103980851B (en) * | 2013-10-16 | 2015-05-20 | 上海华信摩擦材料有限公司 | Brake shoe adhesive resin used for rail transit vehicles, and preparation method thereof |
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