CN110003446A - A kind of light color and high softening-point terpene phenol resin and the preparation method and application thereof - Google Patents
A kind of light color and high softening-point terpene phenol resin and the preparation method and application thereof Download PDFInfo
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- CN110003446A CN110003446A CN201910216201.8A CN201910216201A CN110003446A CN 110003446 A CN110003446 A CN 110003446A CN 201910216201 A CN201910216201 A CN 201910216201A CN 110003446 A CN110003446 A CN 110003446A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
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Abstract
The invention discloses a kind of light color and high softening-point terpene phenol resins, shown in structural formula such as formula (I).Its raw material terpenes of light color and high softening-point terpene phenol resin of the present invention is natural reproducible resource, and abundance is cheap, environment-protecting clean；The adherence and intensity that adhesive can be improved, can be widely used in butadiene-styrene rubber, in the rubber products such as natural rubber and neoprene, can play excellent Efficient Adhesive Promotion.The invention also discloses the preparation methods of the light color and high softening-point terpene phenol resin, and the preparation method is simple, and aggregated-washing-distillation can be prepared；Catalyst amount is few, and is dissolved in solvent, and such post-processing is simple, basic without corrosion and environmental pollution；It can solve the problems, such as that color of resin depth and softening point are relatively low in terpene phenolic synthesis process.Purposes the invention also discloses the light color and high softening-point terpene phenol resin as rubber tackifier or tire additive.
Description
Technical field
The present invention relates to a kind of terpene phenol resins and the preparation method and application thereof, and in particular to a kind of light color and high softening-point terpene
Alkene phenol resin and the preparation method and application thereof.
Background technique
China's turpentine oil annual output occupies first place in the world, and the fine chemical product of high added value is produced using turpentine oil as raw material,
Meet the strategy of sustainable development, there is important economic value and research significance.Wherein with turpentine oil or firpene and phenolic material
The terpene phenol resin that matter is prepared through copolycondensation is exactly Typical Representative therein.The resinoid has good fast light and heat resistance,
And contain phenol structure unit so that its intramolecular interaction it is more common polyterpene resin it is increasingly complex, so as to cause its tool
There are the performance and application different from the latter.Terpene phenol resin and many natural and synthesis macromolecule have good compatibility, are third
The excellent tackifier of olefin(e) acid resin, butadiene-styrene rubber, natural rubber and neoprene etc. are widely used in thermosol, pressure-sensitive
The industry such as adhesive, coating, ink, printed circuit, plastics, rubber product.
According to specific use demand, terpene phenol resin can be via single firpene (such as australene, nopinene, limonene
Deng) either the phenolic substancess such as turpentine oil and phenol the strong acid such as sulfuric acid, benzene sulfonic acid, polyphosphoric acid or ferric trichloride, alchlor,
The Lewis acid catalyst such as boron trifluoride and its complex compound acts on lower polycondensation and is prepared into the resin of different softening point range.In addition,
The resinoid can also be added other active constituents and be modified, such as by dicyclopentadiene (Dicyclopentadiene, DCPD)
It is reacted in incorporation terpene phenol resin, obtains the terpene phenolic modified resin of a kind of DCPD bridging.
Terpene phenol resin is due to having nonpolar terpenes group and polar phenolic hydroxyl group concurrently, so that it is compared to traditional terpene
Olefine resin has widely compatibility, especially has excellent compatibility with polar polymer, market is for terpenes phenolic product
Demand is very big.Based on this, China starts to study it in the middle and later periods in 20th century, but makes little progress, at present mainly by
Terpenes and phenols are subjected to cationic polymerization under the catalyst actions such as Lewis acid and obtained, since catalyst activity is stronger, in solvent
In it is unstable and easily occur terminate reaction, it is lower so as to cause polymerization efficiency, in order to improve polymerization efficiency, generally increase catalyst
Dosage both causes catalyst to waste in this way, influences later period catalyst treatment, environmental pollution, and color of resin is caused to be deepened, and is
Reduction color of resin is generally polymerize using low temperature without influencing yield, but since phenolic substances and australene are poly-
It needs to overcome higher energy fort when conjunction, so they are difficult to activate and effectively polymerize under lower temperature, so as to cause resin production
Rate is lower, so terpene phenolic reaction process generally requires higher temperature to increase polymerization efficiency, but under hot conditions, causes to set
It can accelerate the transfer of polymer chain while rouge color burn, so as to cause degree of polymerization reduction, molecular weight becomes smaller, and eventually leads to tree
Rouge softening point is relatively low.Just due to these problems, the terpene phenol resin color developed at present is generally higher than No. 6 colors, and softening point is small
In 140 DEG C, to limit its use scope and value.Therefore, a kind of light color and high softening-point terpene resin is researched and developed with important
Economic value and research significance.
Summary of the invention
A kind of color (solid Ghana color) is provided it is an object of the invention to overcome the shortcomings of the prior art place
Less than No. 4 colors, softening point are greater than 155 DEG C of light color and high softening-point terpene phenol resin and the preparation method and application thereof.
To achieve the above object, the technical scheme adopted by the invention is as follows: a kind of light color and high softening-point terpene phenol resin, knot
Shown in structure formula such as formula (I):
Wherein, n is the degree of polymerization, and is the integer more than or equal to 1.
The adherence and intensity of adhesive can be improved in light color and high softening-point terpene phenol resin of the present invention.In addition, such
Resin is widely used in butadiene-styrene rubber, in the rubber products such as natural rubber and neoprene, can play excellent thickening effect
Fruit.Especially as tire tread additive can effectively increase tire in low temperature damped coefficient and reduce it at high temperature
Damped coefficient, thus the active balance wet skid and rolling resistance of tire, at the same time, due to higher softening point and
Compatibility can effectively improve glass transition temperature and improve the dynamic storage modulus at 60 DEG C, to provide excellent
Wearability and control stability.
Another object of the present invention, which also resides in, provides the preparation method of the light color and high softening-point terpene phenol resin, including with
Lower step:
(1) first light-colored agent, phenolic substances, partial catalyst and part co-catalyst are added into organic solvent, stirs
It mixes uniformly, during terpenoid substance is added dropwise, remaining catalyst and co-catalyst is added, react, obtain reaction product；
(2) reaction product obtained by step (1) is washed, stratification, collects organic phase, second batch light color is added
Agent removes solvent, adds third batch light-colored agent, is then evaporated under reduced pressure to get the light color and high softening-point terpene phenolic tree
Rouge；
The co-catalyst is organic electronic donor.
The conduct of organic electronic donor is added during the preparation process and helps for light color and high softening-point terpene phenol resin of the present invention
Catalyst can carry out complex reaction with catalyst, more stable catalyst system be formed, when can effectively extend catalyst
Between, alleviate the problem of poor catalyst stability, reactive species are few, and catalytic efficiency is low, resin low yield, is conducive to polymer chain growth
High-molecular compound is formed, the dosage of catalyst furthermore can also be reduced, and color of resin is avoided to deepen.By being added in three batches
Light-colored agent can make terpene phenol resin obtained of light color, color (solid Ghana color) less than No. 4 colors.It can solve terpene phenolic tree
The relatively low problem of rouge softening point.
Preferably, in step (1), the partial catalyst is the 1/5~1/2 of total catalyst quality, and the part, which helps, urges
Agent is the 1/5~1/2 of total co-catalyst quality；Terpenoid substance be added dropwise the total terpenoid substance quality of quality Zhan 1/5~
After 1/2, the co-catalyst of the catalyst and the total co-catalyst quality 1/5~1/2 of Zhan that account for total catalyst quality 1/5~1/2 is added,
Adding manner according to this, until terpenoid substance, catalyst and co-catalyst add completely.Due to catalyst activity of the invention
By force, easily occur to terminate with other materials and react, lead to that catalytic efficiency is low, inactivation, therefore use and repeatedly add catalyst and co-catalysis
The mode of agent, available uniform reactivity concentration, stable catalyst system are conducive to polymer chain growth, it is easier to
Generate the resin of high molecular weight.
It is highly preferred that 3 batches of equivalent of the catalyst and co-catalyst point are added.
Preferably, at least one in following (a)~(e):
(a) phenolic substances is at least one of phenol, tert-butyl phenol, octyl phenol, hydroquinone and resorcinol；
It is highly preferred that the phenolic substances is phenol；
(b) organic solvent is aromatic hydrocarbon organic solvent；Preferably, the aromatic hydrocarbon organic solvent be benzene, toluene or
Dimethylbenzene.It is highly preferred that the aromatic hydrocarbon organic solvent is toluene；
(c) light-colored agent is at least one of halogen simple substance, metal halide and inorganic phosphor-contained acid；It is highly preferred that
The light-colored agent is halogen simple substance or inorganic phosphor-contained acid；
(d) catalyst is Lewis acid；Preferably, the Lewis acid is BF3、AlCl3、ZrCl4、FeCl3And ZnCl2
At least one of.It is highly preferred that the Lewis acid is BF3；
(e) organic electronic donor is ethyl benzoate, ethyl acetate, dimethyl terephthalate (DMT), cyclohexanone, tetrahydro furan
At least one of mutter with benzyl chloride；Preferably, the organic electronic donor is ethyl benzoate.
Preferably, terpenoid substance is to refine the terpenoid substance being dried in the step (1)；The purification drying
The method of processing are as follows: untreated terpenoid substance is subjected to gradually heating and is distilled, 154 DEG C~180 DEG C of fraction is collected, is added
Desiccant handles 18~36h, and the terpenoid substance that filtrate is dried to get the purification is collected in filtering.The desiccant is
Anhydrous calcium chloride.Terpenoid substance is dried by above-mentioned purification, can increase polymerizable raw material activity.
Preferably, the untreated terpenoid substance is in turpentine oil, australene, nopinene, limonene and dipentene
It is at least one.It is highly preferred that the untreated terpenoid substance is at least one of turpentine oil and australene.
Preferably, the turpentine oil is at least one of gum turpentine, steam-distilled turpentine and sulfate turpentine.It is preferred that
Ground, the gum turpentine are at least one of horse hair turpentine oil, wetland turpentine oil and Simao turpentine oil.
Preferably, the untreated terpenoid substance is horse hair turpentine oil, wetland turpentine oil, Simao turpentine oil and australene
At least one of alkene.It is highly preferred that the untreated terpenoid substance is at least one in horse hair turpentine oil and australene
Kind.Most preferably, the untreated terpenoid substance is the mixture or australene of horse hair turpentine oil and australene.Inventor
It was found that reactivity temperature and phenol reactant active temperature are close when terpenoid substance is is main with australene content, use
Its for primary raw material can two class reactive material activity of equilibrium, form high activity comonomer, advantageously form macromolecule terpene phenolic
Polymer.
Preferably, the additive amount of the phenolic substances is the 15%~50% of phenolic substances and terpenoid substance gross mass；
The additive amount of the terpenoid substance is the 50%~85% of phenolic substances and terpenoid substance gross mass.It can be more using the proportion
The effectively reactivity ratio of both balances, enables it to the copolymerization product for preferably forming high molecular weight rather than molecular weight is lower certainly
Aggressiveness.
At least one of preferably, following (A)~D) in:
(A) additive amount of the catalyst is the 0.5%~5% of phenolic substances and terpenoid substance gross mass；
(B) additive amount of the co-catalyst is the 1%~10% of catalyst quality；
(C) additive amount of the light-colored agent is 2 ‰~the 1% of phenolic substances and terpenoid substance gross mass；
(D) mass ratio of first described light-colored agent, second batch light-colored agent and third batch light-colored agent are as follows: 5:4~6:4~
6, it is highly preferred that the mass ratio of first described light-colored agent, second batch light-colored agent and third batch light-colored agent are as follows: 1:1:1.
Preferably, in step (1), the condition of the reaction are as follows: reaction temperature be 20 DEG C~50 DEG C, the reaction time be 2~
5h。
Polymerization reaction is occurred using above-mentioned temperature, had both avoided efficiently abolishing phenolic substances under lower temperature (such as 0 DEG C)
And the higher energy fort that australene is required in polymerization, raw material is difficult to effective activation and participates in reaction, so that the problem of yield is lower, and
And under the conditions of also having evaded high temperature (such as 60 DEG C), rate of polymerization is too fast, and polymer chain transfer increases, and the degree of polymerization reduces, polymer
The problem of molecular weight becomes smaller, and resin softening point is relatively low and color of resin is deepened.
It is highly preferred that the condition of the reaction are as follows: reaction temperature is 30 DEG C~40 DEG C, and the reaction time is 3~4h.Using upper
Reaction temperature is stated, condition is more mild, and color of resin is more shallow.
The object of the invention is also to provide the light color and high softening-point terpene phenol resins as rubber tackifier or tire
The purposes of additive.
The light color and high softening-point terpene phenol resin both can apply to the industry such as coating, ink, printed circuit, plastics,
It can be used as butadiene-styrene rubber, the excellent tackifier of the rubber products such as natural rubber and neoprene improve its Efficient Adhesive Promotion, especially make
For the additive of tire tread, tire wear can be effectively improved, prevent wet and slippery and rolling resistance, it is deep to have expanded turpentine oil/firpene
Processing and application range.
The beneficial effects of the present invention are: the present invention provides a kind of light color and high softening-point terpene phenol resin, institute of the present invention
Stating its raw material terpenes of light color and high softening-point terpene phenol resin is natural reproducible resource, and abundance is cheap, and environmental protection is clear
It is clean；The adherence and intensity of adhesive can be improved in light color and high softening-point terpene phenol resin of the present invention, can be widely used in
In the rubber products such as butadiene-styrene rubber, natural rubber and neoprene, excellent Efficient Adhesive Promotion can be played.The present invention also provides
The preparation method of the light color and high softening-point terpene phenol resin, the preparation method is simple, and aggregated-washing-distillation can make
It is standby；In addition, catalyst amount is few, and is dissolved in solvent, such post-processing is simple, basic without corrosion and environmental pollution；
And it is able to solve color of resin depth in terpene phenolic synthesis process and the relatively low problem of softening point.The present invention also provides described
Purposes of the light color and high softening-point terpene phenol resin as rubber tackifier or tire additive.
Detailed description of the invention
Fig. 1 is the ultraviolet spectra of terpene phenol resin, raw material horse hair turpentine oil and phenol described in embodiment 1, wherein 1 represents
Horse hair turpentine oil；2 represent phenol；3 represent terpene phenol resin；
Fig. 2 is the infrared spectroscopy of terpene phenol resin, raw material horse hair turpentine oil and phenol described in embodiment 1, wherein 1 represents
Horse hair turpentine oil；2 represent phenol；3 represent terpene phenol resin.
Specific embodiment
The structural formula of the preparation method of light color and high softening-point terpene phenol resin described in the embodiment of the present invention such as formula (I) institute
Show:
Wherein, n is the degree of polymerization, and is the integer more than or equal to 1.
In embodiment, terpenoid substance is all made of the terpenoid substance of standing and drying processing, at used purification is dried
The method of reason is identical, comprising the following steps: untreated terpenoid substance is carried out gradually heating and is distilled, collects 154 DEG C~180
DEG C fraction, be added anhydrous calcium chloride processing for 24 hours, filtering, collect filtrate to get it is described purification be dried terpenes object
Matter.
To better illustrate the object, technical solutions and advantages of the present invention, below in conjunction with specific embodiment to the present invention
It is described further.
Embodiment 1
A kind of embodiment of the preparation method of light color and high softening-point terpene phenol resin of the present invention, comprising the following steps:
(1) in the dry four-hole boiling flask of the 1000mL equipped with blender, thermometer, calcium chloride tube and constant pressure funnel
In, 1.50g BF is added3, 45g phenol, 300mL dry toluene and the inorganic phosphor-contained sour light-colored agent of 0.80g, while using micro-injection
Device injects 0.05g ethyl benzoate, is placed in low-temperature circulating pump, leads to N2Air-discharging opens stirring, burns by the way that constant pressure funnel is past
255g purification horse hair turpentine oil is slowly added dropwise in bottle, controls reaction temperature at 30 DEG C, horse hair turpentine oil to be refined has been added dropwise 1/3
Afterwards, 1.50g BF is supplemented3And 0.05g ethyl benzoate, 1.50g BF is supplemented after refining horse hair turpentine oil and dripping 2/33And
0.05g ethyl benzoate continues to drip remaining purification horse hair turpentine oil, after being added dropwise, continues insulation reaction 3h；
(2) after completion of the reaction, four-hole boiling flask is removed, is washed 3 times with 75 DEG C of hot water, stratification, organic phase is collected, is added
The inorganic phosphor-contained sour light-colored agent of 0.80g, is distilled off solvent and remaining water, adds the inorganic phosphor-contained sour light-colored agent of 0.80g, heating
Remove remaining solvent, unreacted raw material and low molecular weight substance to 260 DEG C of vacuum distillations to get terpene phenol resin product,
Color 3-, 155 DEG C of softening point.
Embodiment 2
A kind of embodiment of the preparation method of light color and high softening-point terpene phenol resin of the present invention, comprising the following steps:
(1) in the dry four-hole boiling flask of the 1000mL equipped with blender, thermometer, calcium chloride tube and constant pressure funnel
In, 2.50g BF is added3, 150g phenol, 300mL dry toluene and the inorganic phosphor-contained sour light-colored agent of 0.60g, while using micro-injection
Device injects 0.10g ethyl benzoate, is placed in low-temperature circulating pump, leads to N2Air-discharging opens stirring, burns by the way that constant pressure funnel is past
150g purification horse hair turpentine oil is slowly added dropwise in bottle, controls reaction temperature at 40 DEG C, horse hair turpentine oil to be refined drips 1/3 benefit
Fill 2.50g BF3And 0.10g ethyl benzoate, 2.50g BF is supplemented after refining horse hair turpentine oil and dripping 2/33And 0.10g
Ethyl benzoate continues to drip remaining purification horse hair turpentine oil, after being added dropwise, continues insulation reaction 3.5h；
(2) after completion of the reaction, four-hole boiling flask is removed, is washed 3 times with 75 DEG C of hot water, stratification, organic phase is collected, is added
The inorganic phosphor-contained sour light-colored agent of 0.60g, is distilled off solvent and remaining water, adds the inorganic phosphor-contained sour light-colored agent of 0.60g, heating
Remove remaining solvent, unreacted raw material and low molecular weight substance to 260 DEG C of vacuum distillations to get terpene phenol resin product,
Color 3+, 155.5 DEG C of softening point.
Embodiment 3
A kind of embodiment of the preparation method of light color and high softening-point terpene phenol resin of the present invention, comprising the following steps:
(1) in the dry four-hole boiling flask of the 1000mL equipped with blender, thermometer, calcium chloride tube and constant pressure funnel
In, 3.50g BF is added3, 135g phenol, 300mL dry toluene and the inorganic phosphor-contained sour light-colored agent of 0.40g, while using micro-injection
Device injects 0.14g ethyl benzoate, is placed in low-temperature circulating pump, leads to N2Air-discharging opens stirring, burns by the way that constant pressure funnel is past
165g purification horse hair turpentine oil is slowly added dropwise in bottle, controls reaction temperature at 40 DEG C, horse hair turpentine oil to be refined drips 1/3 benefit
Fill 3.50g BF3And 0.14g ethyl benzoate, 3.50g BF is supplemented after refining horse hair turpentine oil and dripping 2/33And 0.14g
Ethyl benzoate continues to drip remaining purification horse hair turpentine oil, after being added dropwise, continues insulation reaction 4h；
(2) after completion of the reaction, four-hole boiling flask is removed, is washed 3 times with 75 DEG C of hot water, stratification, organic phase is collected, is added
The inorganic phosphor-contained sour light-colored agent of 0.40g, is distilled off solvent and remaining water, adds the inorganic phosphor-contained sour light-colored agent of 0.40g, heating
Remove remaining solvent, unreacted raw material and low molecular weight substance to 260 DEG C of vacuum distillations to get terpene phenol resin product,
Color 3.5,157 DEG C of softening point.
Embodiment 4
A kind of embodiment of the preparation method of light color and high softening-point terpene phenol resin of the present invention, comprising the following steps:
(1) in the dry four-hole boiling flask of the 1000mL equipped with blender, thermometer, calcium chloride tube and constant pressure funnel
In, 3.50g BF is added3, 75g phenol, 300mL dry toluene and the inorganic phosphor-contained sour light-colored agent of 0.80g, while using micro-injection
Device injects 0.17g ethyl benzoate, is placed in low-temperature circulating pump, leads to N2Air-discharging opens stirring, burns by the way that constant pressure funnel is past
225g purification horse hair turpentine oil is slowly added dropwise in bottle, controls reaction temperature at 40 DEG C, horse hair turpentine oil to be refined drips 1/3 benefit
Fill 3.50g BF3And 0.17g ethyl benzoate, 3.50g BF is supplemented after refining horse hair turpentine oil and dripping 2/33And 0.17g
Ethyl benzoate continues to drip remaining purification horse hair turpentine oil, after being added dropwise, continues insulation reaction 4h；
After completion of the reaction, four-hole boiling flask is removed, is washed 3 times with 75 DEG C of hot water, stratification, organic phase is collected, is added
The inorganic phosphor-contained sour light-colored agent of 0.80g, is distilled off solvent and remaining water, adds the inorganic phosphor-contained sour light-colored agent of 0.80g, heating
Remove remaining solvent, unreacted raw material and low molecular weight substance to 260 DEG C of vacuum distillations to get terpene phenol resin product,
Color 3+, 160 DEG C of softening point.
Embodiment 5
A kind of embodiment of the preparation method of light color and high softening-point terpene phenol resin of the present invention, comprising the following steps:
(2) in the dry four-hole boiling flask of the 1000mL equipped with blender, thermometer, calcium chloride tube and constant pressure funnel
In, 3.50g BF is added3, 105g phenol, 300mL dry toluene and the inorganic phosphor-contained sour light-colored agent of 0.60g, while using micro-injection
Device injects 0.17g ethyl benzoate, is placed in low-temperature circulating pump, leads to N2Air-discharging opens stirring, burns by the way that constant pressure funnel is past
195g purification Simao turpentine oil is slowly added dropwise in bottle, controls reaction temperature at 35 DEG C, Simao turpentine oil to be refined drips 1/3 benefit
Fill 3.50g BF3And 0.17g ethyl benzoate, 3.50g BF is supplemented after refining Simao turpentine oil and dripping 2/33And 0.17g
Ethyl benzoate continues to drip remaining purification Simao turpentine oil, after being added dropwise, continues insulation reaction 4h；
(3) after completion of the reaction, four-hole boiling flask is removed, is washed 3 times with 75 DEG C of hot water, stratification, organic phase is collected, is added
The inorganic phosphor-contained sour light-colored agent of 0.60g, is distilled off solvent and remaining water, adds the inorganic phosphor-contained sour light-colored agent of 0.60g, heating
Remove remaining solvent, unreacted raw material and low molecular weight substance to 260 DEG C of vacuum distillations to get terpene phenol resin product,
Color 4,157.5 DEG C of softening point.
Embodiment 6
A kind of embodiment of the preparation method of light color and high softening-point terpene phenol resin of the present invention, comprising the following steps:
(1) in the dry four-hole boiling flask of the 1000mL equipped with blender, thermometer, calcium chloride tube and constant pressure funnel
In, 3.50g BF is added3, 150g phenol, 300mL dry toluene and 0.60g halogen simple substance light-colored agent, while using micro syringe
0.14g ethyl benzoate is injected, low-temperature circulating pump is placed in, leads to N2Air-discharging opens stirring, by constant pressure funnel toward flask
In be slowly added dropwise 150g purification wetland turpentine oil, control reaction temperature at 35 DEG C, wetland turpentine oil to be refined drips 1/3 supplement
3.50g BF3And 0.14g ethyl benzoate, 3.50g BF is supplemented after refining wetland turpentine oil and dripping 2/33And 0.14g benzene
Ethyl formate continues to drip remaining purification wetland turpentine oil, after being added dropwise, continues insulation reaction 4h；
(2) after completion of the reaction, four-hole boiling flask is removed, is washed 3 times with 75 DEG C of hot water, stratification, organic phase is collected, is added
0.60g halogen simple substance light-colored agent, is distilled off solvent and remaining water, adds 0.60g halogen simple substance light-colored agent, is warming up to
260 DEG C of vacuum distillations remove remaining solvent, unreacted raw material and low molecular weight substance to get terpene phenol resin product, face
Color 4,155 DEG C of softening point.
Embodiment 7
A kind of embodiment of the preparation method of light color and high softening-point terpene phenol resin of the present invention, comprising the following steps:
(1) in the dry four-hole boiling flask of the 1000mL equipped with blender, thermometer, calcium chloride tube and constant pressure funnel
In, 1.50g BF is added3, 45g phenol, 300mL dry toluene and the inorganic phosphor-contained sour light-colored agent of 0.80g, while using micro-injection
Device injects 0.05g ethyl benzoate, is placed in low-temperature circulating pump, leads to N2Air-discharging opens stirring, burns by the way that constant pressure funnel is past
255g purification australene is slowly added dropwise in bottle, controls reaction temperature at 35 DEG C, australene to be refined drips 1/3 supplement 1.50g
BF3And 0.05g ethyl benzoate, 1.50g BF is supplemented after refining australene and dripping 2/33And 0.05g ethyl benzoate,
Continue to drip remaining purification australene, after being added dropwise, continues insulation reaction 3h；
(2) after completion of the reaction, four-hole boiling flask is removed, is washed 3 times with 75 DEG C of hot water, stratification, organic phase is collected, is added
The inorganic phosphor-contained sour light-colored agent of 0.80g, is distilled off solvent and remaining water, adds the inorganic phosphor-contained sour light-colored agent of 0.80g, heating
Remove remaining solvent, unreacted raw material and low molecular weight substance to 260 DEG C of vacuum distillations to get terpene phenol resin product,
Color 3+, 157 DEG C of softening point.
Embodiment 8
A kind of embodiment of the preparation method of light color and high softening-point terpene phenol resin of the present invention, comprising the following steps:
(3) in the dry four-hole boiling flask of the 1000mL equipped with blender, thermometer, calcium chloride tube and constant pressure funnel
In, 2.50g BF is added3, 150g phenol, 300mL dry toluene and the inorganic phosphor-contained sour light-colored agent of 0.80g, while using micro-injection
Device injects 0.14g ethyl benzoate, is placed in low-temperature circulating pump, leads to N2Air-discharging opens stirring, burns by the way that constant pressure funnel is past
150g purification australene is slowly added dropwise in bottle, controls reaction temperature at 40 DEG C, australene to be refined drips 1/3 supplement 2.50g
BF3And 0.14g ethyl benzoate, 2.50g BF is supplemented after refining australene and dripping 2/33And 0.14g ethyl benzoate,
Continue to drip remaining purification australene, after being added dropwise, continues insulation reaction 4h；
(4) after completion of the reaction, four-hole boiling flask is removed, is washed 3 times with 75 DEG C of hot water, stratification, organic phase is collected, is added
The inorganic phosphor-contained sour light-colored agent of 0.80g, is distilled off solvent and remaining water, adds the inorganic phosphor-contained sour light-colored agent of 0.80g, heating
Remove remaining solvent, unreacted raw material and low molecular weight substance to 260 DEG C of vacuum distillations to get terpene phenol resin product,
Color 3+, 158 DEG C of softening point.
Embodiment 9
A kind of embodiment of the preparation method of light color and high softening-point terpene phenol resin of the present invention, comprising the following steps:
(3) in the dry four-hole boiling flask of the 1000mL equipped with blender, thermometer, calcium chloride tube and constant pressure funnel
In, 3.50g BF is added3, 135g phenol, 300mL dry toluene and the inorganic phosphor-contained sour light-colored agent of 0.80g, while using micro-injection
Device injects 0.17g ethyl benzoate, is placed in low-temperature circulating pump, leads to N2Air-discharging opens stirring, burns by the way that constant pressure funnel is past
165g purification horse hair turpentine oil is slowly added dropwise in bottle, controls reaction temperature at 35 DEG C, horse hair turpentine oil to be refined drips 1/3 benefit
Fill 3.50g BF3And 0.17g ethyl benzoate, 3.50g BF is supplemented after refining horse hair turpentine oil and dripping 2/33And 0.17g
Ethyl benzoate continues to drip remaining purification horse hair turpentine oil, after being added dropwise, continues insulation reaction 4h；
(4) after completion of the reaction, four-hole boiling flask is removed, is washed 3 times with 75 DEG C of hot water, stratification, organic phase is collected, is added
The inorganic phosphor-contained sour light-colored agent of 0.80g, is distilled off solvent and remaining water, adds the inorganic phosphor-contained sour light-colored agent of 0.80g, heating
Remove remaining solvent, unreacted raw material and low molecular weight substance to 260 DEG C of vacuum distillations to get terpene phenol resin product,
Color 3.5,159 DEG C of softening point.
Embodiment 10
A kind of embodiment of the preparation method of light color and high softening-point terpene phenol resin of the present invention, comprising the following steps:
(1) in the dry four-hole boiling flask of the 1000mL equipped with blender, thermometer, calcium chloride tube and constant pressure funnel
In, 3.50g BF is added3, 75g phenol, 300mL dry toluene and the inorganic phosphor-contained sour light-colored agent of 0.8g, while using micro syringe
0.17g ethyl benzoate is injected, low-temperature circulating pump is placed in, leads to N2Air-discharging opens stirring, by constant pressure funnel toward flask
In be slowly added dropwise 225g purification australene, control reaction temperature at 40 DEG C, australene to be refined drips 1/3 supplement 3.50g
BF3And 0.17g ethyl benzoate, 3.50g BF is supplemented after refining australene and dripping 2/33And 0.17g ethyl benzoate,
Continue to drip remaining purification australene, after being added dropwise, continues insulation reaction 4h；
(2) after answering, four-hole boiling flask is removed, is washed 3 times with 75 DEG C of hot water, stratification, collect organic phase, be added
The inorganic phosphor-contained sour light-colored agent of 0.80g, is distilled off solvent and remaining water, adds the inorganic phosphor-contained sour light-colored agent of 0.80g, heating
Remove remaining solvent, unreacted raw material and low molecular weight substance to 260 DEG C of vacuum distillations to get terpene phenol resin product,
Color 3.5,163.5 DEG C of softening point.
Embodiment 11
A kind of embodiment of the preparation method of light color and high softening-point terpene phenol resin of the present invention, comprising the following steps:
(3) in the dry four-hole boiling flask of the 1000mL equipped with blender, thermometer, calcium chloride tube and constant pressure funnel
In, 2.50g BF is added3, 150g phenol, 300mL dry toluene and the inorganic phosphor-contained sour light-colored agent of 0.6g, while using micro-injection
Device injects 0.17g ethyl benzoate, is placed in low-temperature circulating pump, leads to N2Air-discharging opens stirring, burns by the way that constant pressure funnel is past
150g purification australene is slowly added dropwise in bottle, controls reaction temperature at 35 DEG C, australene to be refined drips 1/3 supplement 2.50g
BF3And 0.17g ethyl benzoate, 2.50g BF is supplemented after refining australene and dripping 2/33And 0.17g ethyl benzoate,
Continue to drip remaining purification australene, after being added dropwise, continues insulation reaction 4h；
(4) after answering, four-hole boiling flask is removed, is washed 3 times with 75 DEG C of hot water, stratification, collect organic phase, be added
The inorganic phosphor-contained sour light-colored agent of 0.60g, is distilled off solvent and remaining water, adds the inorganic phosphor-contained sour light-colored agent of 0.60g, heating
Remove remaining solvent, unreacted raw material and low molecular weight substance to 260 DEG C of vacuum distillations to get terpene phenol resin product,
Color 4-, 158.5 DEG C of softening point.
Embodiment 12
A kind of embodiment of the preparation method of light color and high softening-point terpene phenol resin of the present invention, comprising the following steps:
(1) in the dry four-hole boiling flask of the 1000mL equipped with blender, thermometer, calcium chloride tube and constant pressure funnel
In, 3.50g BF is added3, 75g phenol, 300mL dry toluene and the inorganic phosphor-contained sour light-colored agent of 0.8g, while using micro syringe
0.10g ethyl benzoate is injected, low-temperature circulating pump is placed in, leads to N2Air-discharging opens stirring, by constant pressure funnel toward flask
In 225g purification mixing terpenes (horse hair turpentine oil and australene mass ratio be 1:1) is slowly added dropwise, control reaction temperature at 35 DEG C,
1/3 supplement 3.50g BF is dripped wait refine mixing terpenes3And 0.10g ethyl benzoate, 2/3 is dripped wait refine mixing terpenes
After be supplemented 3.50g BF3And 0.10g ethyl benzoate, continue to drip remaining purification mixing terpenes, after being added dropwise, after
Continuous insulation reaction 4h；
(2) after answering, four-hole boiling flask is removed, is washed 3 times with 75 DEG C of hot water, stratification, collect organic phase, be added
The inorganic phosphor-contained sour light-colored agent of 0.80g, is distilled off solvent and remaining water, adds the inorganic phosphor-contained sour light-colored agent of 0.80g, heating
Remove remaining solvent, unreacted raw material and low molecular weight substance to 260 DEG C of vacuum distillations to get terpene phenol resin product,
Color 3,161 DEG C of softening point.
Embodiment 13
A kind of embodiment of the preparation method of light color and high softening-point terpene phenol resin of the present invention, comprising the following steps:
(1) in the dry four-hole boiling flask of the 1000mL equipped with blender, thermometer, calcium chloride tube and constant pressure funnel
In, 3.50g BF is added3, 75g phenol, 300mL dry toluene and the inorganic phosphor-contained sour light-colored agent of 0.8g, while using micro syringe
0.14g ethyl benzoate is injected, low-temperature circulating pump is placed in, leads to N2Air-discharging opens stirring, by constant pressure funnel toward flask
In 225g purification mixing terpenes (horse hair turpentine oil and australene mass ratio be 2:1) is slowly added dropwise, control reaction temperature at 40 DEG C,
1/3 supplement 3.50g BF is dripped wait refine mixing terpenes3And 0.14g ethyl benzoate, 2/3 is dripped wait refine mixing terpenes
After be supplemented 3.50g BF3And 0.14g ethyl benzoate, continue to drip remaining purification mixing terpenes, after being added dropwise, after
Continuous insulation reaction 4h；
(2) after answering, four-hole boiling flask is removed, is washed 3 times with 75 DEG C of hot water, stratification, collect organic phase, be added
The inorganic phosphor-contained sour light-colored agent of 0.80g, is distilled off solvent and remaining water, adds the inorganic phosphor-contained sour light-colored agent of 0.80g, heating
Remove remaining solvent, unreacted raw material and low molecular weight substance to 260 DEG C of vacuum distillations to get terpene phenol resin product,
Color 3,160.5 DEG C of softening point.
Embodiment 14
A kind of embodiment of the preparation method of light color and high softening-point terpene phenol resin of the present invention, comprising the following steps:
(1) in the dry four-hole boiling flask of the 1000mL equipped with blender, thermometer, calcium chloride tube and constant pressure funnel
In, 3.50g BF is added3, 75g phenol, 300mL dry toluene and the inorganic phosphor-contained sour light-colored agent of 0.6g, while using micro syringe
0.17g ethyl benzoate is injected, low-temperature circulating pump is placed in, leads to N2Air-discharging opens stirring, by constant pressure funnel toward flask
In 225g purification mixing terpenes (horse hair turpentine oil and australene mass ratio be 1:2) is slowly added dropwise, control reaction temperature at 40 DEG C,
1/3 supplement 3.50g BF is dripped wait refine mixing terpenes3And 0.17g ethyl benzoate, 2/3 is dripped wait refine mixing terpenes
After be supplemented 3.50g BF3And 0.17g ethyl benzoate, continue to drip remaining purification mixing terpenes, after being added dropwise, after
Continuous insulation reaction 4h；
(2) after answering, four-hole boiling flask is removed, is washed 3 times with 75 DEG C of hot water, stratification, collect organic phase, be added
The inorganic phosphor-contained sour light-colored agent of 0.60g, is distilled off solvent and remaining water, adds the inorganic phosphor-contained sour light-colored agent of 0.60g, heating
Remove remaining solvent, unreacted raw material and low molecular weight substance to 260 DEG C of vacuum distillations to get terpene phenol resin product,
Color 3.5,162 DEG C of softening point.
Embodiment 15
The structural characterization of light color and high softening-point terpene phenol resin prepared by the present invention and the measuring method of index of correlation are as follows:
Uv-vis spectra: UV-2550 ultraviolet spectrometer (Japanese Shimadzu), 800~200nm of scanning range；Scanning speed:
Low speed；Scan pattern: single；Slit width: 2.0nm；Light source changes wavelength: 340.8nm.
Infrared spectroscopy: FTIR-8400S Fourier transformation infrared spectrometer (Japanese Shimadzu), using KBr tabletting or liquid modulus method
Sample is measured, 4000~400cm of wave-number range is measured-1；
Color measuring method refers to GB/T 1722-1992 " varnish, edible vegetable oil and diluent colour measurement method "；Softening point
Measuring method refers to GB/T 8146-2003 " Test methods of rosin ".
In order to confirm to prepared light color and high softening-point terpene phenol resin, uv-vis spectra (UV-vis) by with
Such terpene phenol resin is characterized, and comparison raw material terpenes, test results are shown in figure 1 phenol.Due to structure
Similitude, we choose embodiment 1 terpenes phenolic product 1 and feed purification horse hair turpentine oil, phenol carry out test analysis.From
Fig. 1 can observe obviously, belong to horse hair turpentine oil 252nm and belong to the strong characteristic absorption peak warp at the 270nm of phenol
After polymerization reaction, at red shift to 282nm, after showing that terpenes and phenol carry out polymerization reaction, the terpenes group of electron is connected to
On phenol, play the role of helping color.In addition, it can also be seen that only one characteristic absorption peak of polymer terpene phenolic, and
The polymer features absorption peak absorption peak sharp compared to raw material is obviously smoothened, and its reaction raw materials horse hair turpentine oil and benzene
The other feature absorption peak of phenol completely disappears, and shows that such terpene phenol resin is successfully synthesized.
In order to further confirm to prepared light color and high softening-point terpene phenol resin, FTIR spectrum
(FTIR) it is used to characterize such terpene phenol resin, test result such as Fig. 2 with comparison material sample terpenes, phenol
It is shown.Due to the similitude of structure, we choose embodiment 1 terpenes phenolic product 1 and feed purification horse hair turpentine oil, phenol into
Row test analysis.By Fig. 2 it can be found that its 3416cm of product terpenes phenol polymer-1Belong to the stretching vibration of phenol O-H, 2956,
2930、2870cm-1Belong to CH3C-H stretching vibration, 1610~1464cm-1Belong to the skeletal vibration of phenyl ring, 1385,
1366cm-1Belong to-(CH3)2Symmetrical deformation vibration and 1259~1152cm-1Belong to the flexible vibration of aryl oxide Ar-O-C
It is dynamic, it can be obviously observed, after horse hair turpentine oil is reacted with Phenol Polymerization, it is special that product terpene phenolic combines the two classes raw material
The absorption peak of group is levied, and compared to starting monomer, the Partial Feature peak of polymer terpene phenolic disappears or intensity obviously weakens,
Peak shape also it is opposite become it is more flat with it is smooth, this may be in polymer molecule stronger interaction result in intramolecular and transport
It moves caused by being restricted.In conjunction with ultraviolet spectrum data before, it can determine that target terpene phenol resin is successfully synthesized.Due to it
The structure and characterization situation of remaining terpene phenol resin are similar with terpene phenol resin 1 in the above embodiments 1, therefore do not go to live in the household of one's in-laws on getting married one by one herein
It states.
According to above-mentioned test result it is found that method according to the present invention, it is small to successfully synthesize a kind of color (solid Ghana color)
In No. 4 colors, softening point is greater than 155 DEG C of light color and high softening-point terpene phenol resin.And a certain proportion of resinoid is applied to
In hot melt adhesive, test discovery, glue peel strength increase 30%, hold viscosity and increase 15%, be effectively improved under the high temperature conditions
Mechanical property and application power under hot melt adhesive high temperature.And as additive application in tire tread, pass through mechanics
Performance test discovery, compared with the tire tread for being not added with the resinoid, the coefficient of waste improves 4.7%, the resistance under low temperature
Buddhist nun's coefficient improves 5.3%, and the damped coefficient under high temperature reduces 5%, and at the same time, the dynamic storage modulus at 60 DEG C reduces
23%, to provide excellent wear-resisting, anti-skidding, low-rolling-resistance and good processing and control stability.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than protects to the present invention
The limitation of range is protected, although the invention is described in detail with reference to the preferred embodiments, those skilled in the art should
Understand, it can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the essence of technical solution of the present invention
And range.
Claims (10)
1. a kind of light color and high softening-point terpene phenol resin, which is characterized in that shown in its structural formula such as formula (I):
Wherein, n is the degree of polymerization, and is the integer more than or equal to 1.
2. the preparation method of light color and high softening-point terpene phenol resin as described in claim 1, which is characterized in that including following step
It is rapid:
(1) first light-colored agent, phenolic substances, partial catalyst and part co-catalyst are added into organic solvent, stirring is equal
It is even, terpenoid substance is added dropwise, remaining catalyst and co-catalyst is added, reacts, obtains reaction product；
(2) reaction product obtained by step (1) is washed, stratification, collects organic phase, second batch light-colored agent is added, goes
Except solvent, third batch light-colored agent is added, is then evaporated under reduced pressure to get the light color and high softening-point terpene phenol resin；
The co-catalyst is organic electronic donor.
3. the preparation method of light color and high softening-point terpene phenol resin as claimed in claim 2, which is characterized in that following (a)~(e)
At least one of in:
(a) phenolic substances is at least one of phenol, tert-butyl phenol, octyl phenol, hydroquinone and resorcinol；
(b) organic solvent is aromatic hydrocarbon organic solvent；
(c) light-colored agent is at least one of halogen simple substance, metal halide and inorganic phosphor-contained acid；
(d) catalyst is Lewis acid；
(e) the organic electronic donor is ethyl benzoate, ethyl acetate, dimethyl terephthalate (DMT), cyclohexanone, tetrahydro furan
At least one of mutter with benzyl chloride.
4. the preparation method of light color and high softening-point terpene phenol resin as claimed in claim 2, which is characterized in that the step (1)
Middle terpenoid substance is the terpenoid substance that purification is dried；The method that the purification is dried are as follows: by untreated terpene
Alkenes substance carries out gradually heating distillation, collects 154 DEG C~180 DEG C of fraction, and desiccant is added and handles 18~36h, filters, receives
Collect the terpenoid substance that filtrate is dried to get the purification.
5. the preparation method of light color and high softening-point terpene phenol resin as claimed in claim 4, which is characterized in that described untreated
Terpenoid substance is at least one of turpentine oil, australene, nopinene, limonene and dipentene；Preferably, the turpentine oil is
At least one of gum turpentine, steam-distilled turpentine and sulfate turpentine；Preferably, the gum turpentine be horse hair turpentine oil,
At least one of wetland turpentine oil and Simao turpentine oil.
6. the preparation method of light color and high softening-point terpene phenol resin as claimed in claim 4, which is characterized in that described untreated
Terpenoid substance is at least one of horse hair turpentine oil, wetland turpentine oil, Simao turpentine oil and australene；Preferably, described
Untreated terpenoid substance is at least one of horse hair turpentine oil and australene.
7. the preparation method of light color and high softening-point terpene phenol resin as claimed in claim 2, which is characterized in that the phenolic substances
Additive amount be the 15%~50% of phenolic substances and terpenoid substance gross mass；The additive amount of the terpenoid substance is phenols
The 50%~85% of substance and terpenoid substance gross mass.
8. the preparation method of light color and high softening-point terpene phenol resin as claimed in claim 2, which is characterized in that following (A)~D)
At least one of in:
(A) additive amount of the catalyst is the 0.5%~5% of phenolic substances and terpenoid substance gross mass；
(B) additive amount of the co-catalyst is the 1%~10% of catalyst quality；
(C) additive amount of the light-colored agent is 2 ‰~the 1% of phenolic substances and terpenoid substance gross mass；
(D) mass ratio of first described light-colored agent, second batch light-colored agent and third batch light-colored agent are as follows: 5:4~6:4~6.
9. the preparation method of light color and high softening-point terpene phenol resin as claimed in claim 2, which is characterized in that in step (1), institute
State the condition of reaction are as follows: reaction temperature is 20 DEG C~50 DEG C, and the reaction time is 2~5h.
10. purposes of the light color and high softening-point terpene phenol resin as described in claim 1 as rubber tackifier or tire additive.
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| CN112812276A (en) * | 2021-01-19 | 2021-05-18 | 厦门中坤化学有限公司 | Preparation method of rosin modified terpene phenol resin |
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