CN109575208A - A kind of synthetic method of the modified p-tert-butylphenol acetaldehyde resin of methacrylaldehyde - Google Patents
A kind of synthetic method of the modified p-tert-butylphenol acetaldehyde resin of methacrylaldehyde Download PDFInfo
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- CN109575208A CN109575208A CN201811616424.5A CN201811616424A CN109575208A CN 109575208 A CN109575208 A CN 109575208A CN 201811616424 A CN201811616424 A CN 201811616424A CN 109575208 A CN109575208 A CN 109575208A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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Abstract
The invention discloses a kind of synthetic methods of the modified p-tert-butylphenol acetaldehyde resin of methacrylaldehyde, this method is using acetaldehyde and methacrylaldehyde as raw material, they first carry out condensation reaction with p-tert-butylphenol respectively, polycondensation reaction is finally carried out again, double bond is introduced into polymerized monomer by this mode of operation, the modified p-tert-butylphenol acetaldehyde resin of gained methacrylaldehyde not only contains double bond in the end group of strand, in repetitive unit, intramolecule also contain double bond.The increase of double bond improves the degree of branching of product, and double bond can increase persistent sticky with the structural interaction in rubber.The initial viscosity and long-acting viscosity of gained resin of the invention are fine, thickening property is close compared with Koresin resin, and cost is far below Koresin resin, Koresin resin can be replaced to use as rubber tackifying resin, rubber product production cost is reduced, is had a extensive future.
Description
Technical field
The present invention relates to a kind of synthetic methods of tackifying resin, and in particular to a kind of synthesis side of Alkylphenolic Tackifying Resin
Method and application in rubber product field, belong to alkyl phenolic resin technical field.
Background technique
Radial is commonly called as " steel wire tire ", it is body cord by meridian direction arrangement, by cord circumferential array or
Buffer layer close to circumferential array tightly binds round a kind of novel tire on carcass.The adhesive strength of rubber and steel wire is very in tire
The quality of radial-ply tyre is affected in big degree.Therefore, tack is critically important in forming process, thus also referred to as forms viscous
Property.In addition, if lacking viscosity between sizing material, especially for synthetic rubber rubber compound, semi-finished product glue part creep makes size distortion
Expansion when can be because of molding causes glue part to paste position disengagement.In all-steel radial tire product design, tyre bead portion, belt side
The many places such as portion all use sticky preferable thin film, if there is phenomenon is not glued, then shelter air, shadow when will lead to fetus molding
Ring final product quality.
Natural rubber has good tack, thus processing performance is good；Although synthetic rubber has wear-resisting, ageing-resistant
With certain special advantages, but it lacks enough tacks, brings difficulty to moulding process, the mode usually solved first is that plus
Enter tackifying resin to improve viscosity.Tackifying resin should have following four condition: good with the compatibility of rubber mass；Itself has
Very strong adhesiveness；The extension variation of Efficient Adhesive Promotion persistently and at any time is small；The physical of curingprocess rate and vulcanizate is not reduced
Energy.Synthetic resin initial viscosity and persistence are all preferable, so it is using more and more, wherein alkyl phenolic resin effect is the most
It is excellent, have become one of main rubber chemicals kind of tire building.The Koresin resin of German BASF production is long-acting
There is indispensable advantage in terms of thickening aspect and humidity resistance.Koresin resin is synthesized by alkyl phenol and acetylene reaction, the conjunction
It is gas-solid reaction at technique, complex process, technology content require height, involve great expense.Therefore, expensive cost limits
The popularization of Koresin resin is only ever used at present in some high-end products.
The viscosifying mechanisms of Koresin resin are always the hot spot of tackifying resin industry research.The group of C.S.MARVEL and he
Teams' tert-butyl phenol is reacted with acetaldehyde, has synthesized p-tert-butylphenol-acetaldehyde resin, which has with Koresin resin
Similar structure, but its Efficient Adhesive Promotion is not as good as Koresin resin.Currently, being produced to find the substitution of koresin resin
Product, tackifying resin industry have a large amount of research, most common method be terminal groups modification is carried out to alkyl resinox, such as:
The end groups classes such as morpholine is modified, allyl chloride is modified are modified, such modified product mainly to the end group of common alkyl phenolic resin into
Row is modified, such product is often obviously improved the tack of sizing material, and long-acting tackifying performance is poor.
It is modified to tert-butyl-phenyl ether tackifying resin and its preparation that 102391449 A of patent CN discloses a kind of allyl
Method.The resin be on the basis of p-tert-butylphenol-formaldehyde resin, by resin and allyl chloride with 3 ~ 1:0.5 of molar ratio ~
2 mixing, are dissolved with ethyl alcohol, are added potassium hydroxide and are adjusted PH to 8-10, after heating 30-90 min, are extracted with toluene, distilled water
Washing obtains after being evaporated under reduced pressure to neutrality.Data show that the tackifying resin of this method preparation is in tack, thermo-oxidative ageing
Self-adhesion intensity is all improved largely, but lacks long-acting tackifying data.Part phenolic hydroxyl group and allyl in the resin of this method synthesis
Ehter bond is formd between base chlorine, reduces the density of phenolic hydroxyl group, according to the research of C.S.MARVEL et al., this may be to resin
Long-acting tackifying have an adverse effect, meanwhile, which repeatedly washs, complex process, and generates more waste water and have
Machine waste liquid.
10565646806 A of patent CN discloses a kind of preparation of super tackifying resin of alkyl phenol-formaldehyde that acetylene is modified
Method, firstly, then synthesis of alkyl resinox is added zinc polycarboxylate and makees catalyst, with acetylene to alkyl resinox
It is modified, synthesizes super tackifying resin.The patent only gives the indices of modified resin product, lacks application performance
Testing result.It is analyzed from reaction mechanism, the resin structure feature in the patent are as follows: the both ends of alkyl resinox connect
Vinyl with double bond due to steric hindrance only has a small amount of phenolic hydroxyl group and acetylene reaction in the inside of strand
Generate vinyl ethers.It can be seen that the resin and traditional alkyl resinox phase that the patent obtains from the structure of resin
Than being only connected to vinyl structure at endpoint, thickening property improves limited.
It can thus be seen that all being focused on phenolic acid resin terminal groups to the research of alkyl phenolic resin adhesiveness increasing and modifying at present
In modification, other modification modes are had not been reported, and obtained resin property modified at present is below koresin resin, not with
The similar relevant report of koresin resin property, therefore the research of this respect also needs further to work.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of modified p-tert-butylphenol acetaldehyde resins of methacrylaldehyde
Synthetic method, this method is liquid phase reactor, and using p-tert-butylphenol, acetaldehyde and methacrylaldehyde as raw material, reaction condition is mild, nothing
Waste liquid, without solid waste, do not have to washing, concise in technology, at low cost, products obtained therefrom performance is good.
Methacrylaldehyde double bond is introduced into phenolic resin by the present invention using p-tert-butylphenol, acetaldehyde, methacrylaldehyde as raw material, is closed
At the modified p-tert-butylphenol acetaldehyde resin of methacrylaldehyde.The modified p-tert-butylphenol acetaldehyde resin structure of the methacrylaldehyde is special, point
Double bond is had in sub, there is preferable initial viscosity and long-acting viscosity, performance is similar with Koresin resin, can be used as
The substitute of Koresin resin has industrial popularization and application value.
Specific technical solution of the present invention is as follows:
A kind of synthetic method of the modified p-tert-butylphenol acetaldehyde resin of methacrylaldehyde, method includes the following steps:
(1) p-tert-butylphenol and acetaldehyde are subjected to condensation reaction under the action of catalyst；
(2) after step (1), methacrylaldehyde is added into the product of step (1), continues condensation reaction under the action of catalyst；
(3) after step (2), reaction solution is adjusted to neutrality, organic solvent is added and extracts product, gained organic phase is distilled off organic
Solvent and water, then heating carries out polycondensation reaction, obtains the modified p-tert-butylphenol acetaldehyde resin of methacrylaldehyde.
In the above method, the molar ratio of p-tert-butylphenol and acetaldehyde is 1.0:0.8-0.9, preferably 1.0:0.85-
0.9。
In the above method, the quality of methacrylaldehyde is the 5-10% of p-tert-butylphenol quality.
In the above method, condensation reaction needs to carry out in the presence of a catalyst, and catalyst used is acid, and acid can be
Machine acid is also possible to inorganic acid.Acid catalyst used in the present invention can be public using the institute of phenolic resin synthetic technology in the prior art
Any acid catalyst, such as oxalic acid, the concentrated sulfuric acid, p-methyl benzenesulfonic acid for opening etc..Acid can be added in solid form, can also be with water
Solution form is added.The dosage of catalyst can be using the dosage of catalyst in phenolic resin synthesis process in the prior art.
In the above method, acetaldehyde instills in reaction system in form of an aqueous solutions, it is contemplated that water to the adverse effect of reaction,
It is preferred that using highly concentrated aqueous solution, it is preferred that the concentration of acetaldehyde solution is 37-40wt%.Methacrylaldehyde is liquid, is being added
Shi Youxuan is added in the form being added dropwise.
Further, in above-mentioned steps (1), the temperature of condensation reaction is 80 ~ 100 DEG C, preferably 90 ~ 100 DEG C,
Reaction time is preferably 1-3h.In step (2), the temperature of condensation reaction is also 80 ~ 100 DEG C, preferably 90 ~ 100 DEG C,
Reaction time is preferably 1-2h.In step (3), the temperature of polycondensation reaction is 160 ~ 170 DEG C, and the reaction time is preferably 0.5-
2h。
Further, in above-mentioned steps (2), water is first distilled off, adds methacrylaldehyde and is reacted.
Further, after step (2), alkaline matter conditioned response liquid pH is added to neutrality, the alkaline matter can be
Sodium hydroxide, potassium hydroxide etc. are also possible to their aqueous solution.
Further, in above-mentioned steps (3), organic solvent used can be arbitrarily report in the prior art, Ke Yiyong
In the organic solvent of phenolic acid resin preparation, in the specific embodiment of the invention, organic solvent used is toluene, benzene, dimethylbenzene
Deng each organic solvent effect is similar.
The structural formula of the modified p-tert-butylphenol acetaldehyde resin of the methacrylaldehyde that the present invention obtains is as described in following formula, and in formula, R is
CH3Or CH=CH2, CH=CH2And CH3It exists simultaneously in following formula, R is not CH3It is exactly CH=CH2。
。
Further, in the structural formula of the modified p-tert-butylphenol acetaldehyde resin of above-mentioned methacrylaldehyde, n 2,3,4,5 or 6.
Preferably, the weight average molecular weight of the modified p-tert-butylphenol acetaldehyde resin of above-mentioned methacrylaldehyde is preferably 800-1200,
Softening point is preferably 120-150 DEG C.
The invention has the following advantages:
1, the present invention is using acetaldehyde and methacrylaldehyde as raw material, they first carry out condensation reaction with p-tert-butylphenol respectively, then finally
Polycondensation reaction is carried out, double bond is introduced into polymerized monomer by this mode of operation, the modified p-tert-butylphenol second of gained methacrylaldehyde
Urea formaldehyde not only contains double bond in the end group of strand, in repetitive unit, intramolecule also contain double bond.The increase of double bond mentions
The high degree of branching of product, double bond can increase persistent sticky with the structural interaction in rubber.
2, the present invention is modified phenolic resin using methacrylaldehyde, and methacrylaldehyde is added in the condensation stage rather than is forming phenol
It is added after urea formaldehyde, improves the content of double bond.Further, since modified using aldehydes, double bond is connected to the ortho position of phenolic hydroxyl group,
Rather than reacted with phenolic hydroxyl group, it not will lead to the reduction of content of phenolic hydroxyl groups, the group unfavorable to resin viscosity will not be formed, such as
Ehter bond.
3, the initial viscosity and long-acting viscosity of the modified p-tert-butylphenol acetaldehyde resin of methacrylaldehyde of the present invention are fine, with
Koresin resin is close compared to thickening property, and cost is far below Koresin resin, Koresin resin can be replaced as rubber
Tackifying resin uses, and reduces rubber product production cost, has a extensive future.
4, present invention process is simpler compared with Koresin synthetic technology of resins, safe, mild, is not required to wash, will not produce
Raw a large amount of waste water, waste liquid and solid waste, and product cost is lower, has industrial popularization and application value.
5, present invention process is low for equipment requirements, can be completed using the synthesis device of common tackifying resin, saves production
Cost is suitable for industrialization promotion.
Detailed description of the invention
The infrared spectrum of the modified p-tert-butylphenol acetaldehyde resin of 1 gained methacrylaldehyde of Fig. 1 embodiment.
Specific embodiment
Below by specific embodiment, invention is further explained, and following related descriptions are exemplary only, and
Its content is not limited.In following embodiments, p-tert-butylphenol, acetaldehyde, the concentrated sulfuric acid (98wt%) and methacrylaldehyde used etc.
Raw material commercially obtains.
In following embodiments, the concentration is mass concentration unless otherwise instructed.
Embodiment 1
Weigh 100 g(0.67 mol of p-tert-butylphenol), 0.17 g of the concentrated sulfuric acid, be added equipped with mechanical agitator, thermometer, return
In 250 ml, tetra- mouthfuls of round-bottom reaction flasks of flow condenser and dropping funel, 90 DEG C are warming up to, 58.7 g acetaldehyde solutions are added dropwise
(phenol formaldehyde ratio 1:0.8), successive reaction 1 hour.After reaction, 100 DEG C of water steamed in system are warming up to.5.0 g are instilled again
Methacrylaldehyde (0.09 mol), being warming up to 90 DEG C, the reaction was continued 1 hour.After reaction, sodium hydroxide lye (2.5%) is added, adjusts
PH to 6.5 is saved, 80 g toluene are then added, organic phase is extracted, water phase is released.Then, organic phase is distilled off remaining
Water and toluene, then temperature rises to 160 DEG C of progress polycondensations, keeps 0.5 h, discharging is to get the modified p-tert-butylphenol of methacrylaldehyde
Acetaldehyde resin.It will be weighed after product cooling, yield 97%.
The infrared spectrum of products obtained therefrom is as shown in Figure 1, it can be seen from the figure that gained methacrylaldehyde is modified p-tert-butylphenol
The infrared similarity of acetaldehyde resin and Koresin resin is 93.21%, and in 880 cm-1There is very strong absorption peak at place, illustrates point
Contain CH in son2=CH2Structure.
It is 125 DEG C with the softening point that ring and ball softening point instrument measures this resin, measures weight with gel permeation chromatography (GPC) method
Average molecular weight is 885 g/mol, and the mass percentage with the p-tert-butylphenol that dissociates in bromination method measurement resin is 0.6%,
Biodiversity percentage composition is 0.8%.
Embodiment 2
Weigh 100 g(0.67 mol of p-tert-butylphenol), 0.17 g of the concentrated sulfuric acid, be added equipped with mechanical agitator, thermometer, return
In 250 ml, tetra- mouthfuls of round-bottom reaction flasks of flow condenser and dropping funel, 90 DEG C are warming up to, 66.0 g acetaldehyde solutions are added dropwise
(phenol formaldehyde ratio 1:0.9), successive reaction 2 hours.After reaction, 105 DEG C of water steamed in system are warming up to, then instill 5.0 g
Methacrylaldehyde (0.09 mol), being warming up to 90 DEG C, the reaction was continued 1 hour.After reaction, sodium hydroxide lye (2.5%) is added,
PH to 6.5 is adjusted, 80 g toluene are then added, organic phase is extracted, water phase is released.Then, residue is distilled off in organic phase
Water and toluene, then heat to 170 DEG C of progress polycondensations, keep 0.5 h, discharging is to get the modified p-tert-butylphenol of methacrylaldehyde
Acetaldehyde resin.By the cooling weighing of product, yield 96.5%.It is 130 with the softening point that ring and ball softening point instrument measures this resin
DEG C, measuring weight average molecular weight with gel permeation chromatography (GPC) method is 915 g/mol, is dissociated in bromination method measurement resin to uncle
The mass percentage of butylphenol is 0.6%, and biodiversity percentage composition is 0.8%.
Embodiment 3
Weigh 100 g(0.67 mol of p-tert-butylphenol), 0.17 g of the concentrated sulfuric acid, be added equipped with mechanical agitator, thermometer, return
In 250 ml, tetra- mouthfuls of round-bottom reaction flasks of flow condenser and dropping funel, 100 DEG C are warming up to, it is water-soluble that 58.7 g acetaldehyde are added dropwise
Liquid (phenol formaldehyde ratio 1:0.8), successive reaction 1 hour.After reaction, 110 DEG C of water steamed in system are warming up to, are then instilled
10.0 g methacrylaldehyde (0.18 mol), being warming up to 100 DEG C, the reaction was continued 2 hours.After reaction, sodium hydroxide lye is added
(2.5%), PH to 6.5 is adjusted, 80 g toluene are then added, organic phase is extracted, water phase is released.Then, organic phase distillation is removed
Remaining water and toluene are removed, then heats to 160 DEG C, keeps 0.5 h, discharging is to get the modified p-tert-butylphenol second of methacrylaldehyde
Urea formaldehyde.By the cooling weighing of product, yield 98%.It is 122 DEG C with the softening point that ring and ball softening point instrument measures this resin, uses
It is 873 g/mol that gel permeation chromatography (GPC) method, which measures weight average molecular weight, is dissociated in bromination method measurement resin to tert-butyl benzene
The mass percentage of phenol is 0.5%, and biodiversity percentage composition is 0.8%.
Embodiment 4
Weigh 100 g(0.67 mol of p-tert-butylphenol), 0.17 g of the concentrated sulfuric acid, be added equipped with mechanical agitator, thermometer, return
In 250 ml, tetra- mouthfuls of round-bottom reaction flasks of flow condenser and dropping funel, 95 DEG C are warming up to, 66.0 g acetaldehyde solutions are added dropwise
(phenol formaldehyde ratio 1:0.9), successive reaction 1 hour.After reaction, 120 DEG C of water steamed in system are warming up to, then instill 8.0
G methacrylaldehyde (0.144 mol), being warming up to 95 DEG C, the reaction was continued 2 hours.After reaction, sodium hydroxide lye is added
(2.5%), PH to 7.0 is adjusted, 80 g toluene are then added, organic phase is extracted, water phase is released.Then, organic phase distillation is removed
Remaining water and toluene are removed, 160 DEG C of progress polycondensations are then heated to, keeps 0.5 h, discharging is modified to tertiary fourth to get methacrylaldehyde
Base phenol-acetaldehyde resin.By the cooling weighing of product, yield 97%.It is with the softening point that ring and ball softening point instrument measures this resin
138 DEG C, measuring weight average molecular weight with gel permeation chromatography (GPC) method is 935 g/mol, is dissociated in bromination method measurement resin
The mass percentage of p-tert-butylphenol is 0.6%, biodiversity percentage composition 0.6%.
Embodiment 5
The modified p-tert-butylphenol acetaldehyde resin of methacrylaldehyde is prepared according to the method for embodiment 1, unlike: acetaldehyde solution
Dosage is 62.3g(phenol formaldehyde ratio 1:0.85).It is 130 DEG C with the softening point that ring and ball softening point instrument measures this resin, uses gel infiltration
It is 903g/mol that chromatography (GPC) method, which measures weight average molecular weight, with the quality for the p-tert-butylphenol that dissociates in bromination method measurement resin
Percentage composition is 0.6%, biodiversity percentage composition 0.7%.
Embodiment 6
The modified p-tert-butylphenol acetaldehyde resin of methacrylaldehyde is prepared according to the method for embodiment 3, unlike: acetaldehyde solution
Dosage is 66.0 g(phenol formaldehyde ratio 1:0.9).It is 150 DEG C with the softening point that ring and ball softening point instrument measures this resin, uses gel infiltration
It is 1120g/mol that chromatography (GPC) method, which measures weight average molecular weight, with the quality for the p-tert-butylphenol that dissociates in bromination method measurement resin
Percentage composition is 0.5%, biodiversity percentage composition 0.5%.
Comparative example 1
Weigh 100 g(0.67 mol of p-tert-butylphenol), 0.17 g of the concentrated sulfuric acid, be added equipped with mechanical agitator, thermometer, return
In 250 ml, tetra- mouthfuls of round-bottom reaction flasks of flow condenser and dropping funel, 90 DEG C are warming up to, 43.3 g formalins are added dropwise
(phenol formaldehyde ratio 1:0.8), successive reaction 1 hour, after reaction be added sodium hydroxide solution (2.5%) adjust reaction solution PH=7, then plus
Enter 80 g toluene, extracts organic phase, water phase is released.Then, remaining water and toluene is distilled off in organic phase, then heated up
To 160 DEG C, 0.5 h, discharging are kept.By the cooling weighing of product, yield 99%.This resin is measured with ring and ball softening point instrument
Softening point is 131 DEG C, and measuring weight average molecular weight with gel permeation chromatography (GPC) method is 895 g/mol, is measured and is set with bromination method
The mass percentage of free p-tert-butylphenol is 0.6% in rouge, and biodiversity percentage composition is 0.8%.
Comparative example 2
Weigh 100 g(0.67 mol of p-tert-butylphenol), 0.17 g of the concentrated sulfuric acid, be added equipped with mechanical agitator, thermometer, return
In 250 ml, tetra- mouthfuls of round-bottom reaction flasks of flow condenser and dropping funel, 90 DEG C are warming up to, 66.0g acetaldehyde solution (phenol is added dropwise
Aldehyde ratio 1:0.9), successive reaction 2 hours.Sodium hydroxide solution (2.5%) is added after reaction and adjusts the then addition of reaction solution PH=6.5
80 g toluene extract organic phase, water phase are released.Then, remaining water and toluene is distilled off in organic phase, then heated to
170 DEG C, keep 0.5 h, discharging.By the cooling weighing of product, yield 97%.The soft of this resin is measured with ring and ball softening point instrument
Changing point is 127 DEG C, and measuring weight average molecular weight with gel permeation chromatography (GPC) method is 850 g/mol, measures resin with bromination method
In dissociate p-tert-butylphenol mass percentage be 0.5%, biodiversity percentage composition be 0.7%.
Comparative example 3
The synthesis of the modified p-tert-butylphenol-acetaldehyde resin of morpholine, using the concentrated sulfuric acid as acidic catalyst, p-tert-butylphenol,
Acetaldehyde is raw material, p-tert-butylphenol: acetaldehyde (molar ratio)=1:0.8.Morpholine makees modifying agent, structural formula are as follows:。
The specific steps are the same as those in embodiment 1, as follows:
Weigh 100 g(0.67 mol of p-tert-butylphenol), 0.17 g of the concentrated sulfuric acid, be added equipped with mechanical agitator, thermometer, return
In 250 ml, tetra- mouthfuls of round-bottom reaction flasks of flow condenser and dropping funel, 90 DEG C are warming up to, 58.7 g acetaldehyde solutions are added dropwise
(phenol formaldehyde ratio 1:0.8), successive reaction 1 hour.After reaction, 100 DEG C of water steamed in system are warming up to.Add 0.09
The morpholine of mol, being warming up to 90 DEG C, the reaction was continued 1 hour.After reaction, be added sodium hydroxide lye (2.5%), adjust PH to
6.5,80 g toluene are then added, extracts organic phase, water phase is released.Then, remaining water and first is distilled off in organic phase
Benzene, then temperature rises to 160 DEG C of progress polycondensations, keeps 0.5 h, discharging.It will be weighed after product cooling, yield 95%.Use ring
The softening point that ball softening point instrument measures this resin is 131 DEG C, and measuring weight average molecular weight with gel permeation chromatography (GPC) method is
912g/mol, the mass percentage with the p-tert-butylphenol that dissociates in bromination method measurement resin is 0.9%, biodiversity percentage
Content is lower than 1%.
Comparative example 4
Weigh 100 g(0.67 mol of p-tert-butylphenol), 0.17 g of the concentrated sulfuric acid, be added equipped with mechanical agitator, thermometer, return
In 250 ml, tetra- mouthfuls of round-bottom reaction flasks of flow condenser and dropping funel, 90 DEG C are warming up to, 58.7 g acetaldehyde solutions are added dropwise
(phenol formaldehyde ratio 1:0.8), successive reaction 1 hour.After reaction, sodium hydroxide lye (2.5%) is added, adjusts PH to 6.5, so
After be added 80 g toluene, extract organic phase, water phase released.Then, water is distilled off in organic phase, then temperature rises to 160
DEG C carry out polycondensation, keep 0.5 h.80 g toluene are added, then instill 5.0 g methacrylaldehyde (0.09 mol), are warming up to 90 DEG C of continuation
Reaction 1 hour.After reaction, sodium hydroxide lye (2.5%) is added, adjusts PH to 6.5,80 g toluene is then added, extract
Organic phase releases water phase.Then, remaining water and toluene is distilled off in organic phase, then temperature rises to 160 DEG C of progress
Polycondensation, keeps 0.5 h, and discharging will weigh, yield 96% after product cooling.The soft of this resin is measured with ring and ball softening point instrument
Changing point is 121 DEG C, and measuring weight average molecular weight with gel permeation chromatography (GPC) method is 861 g/mol, measures resin with bromination method
In dissociate p-tert-butylphenol mass percentage be 0.5%, biodiversity percentage composition be 0.8%.
Application examples
The above embodiment of the present invention and the resulting resin of comparative example can be used as the use of rubber tackifying resin, in order to verify theirs
Performance carries out following verification test.
Using all-steel load-bearing radial tire shoulder pad glue formula refining glue shown in table 1, compares different tackifying resin samples and answer
With performance, tackifying resin is the resin of each embodiment and comparative example preparation, while purchased from German BASF Chemical Group
Koresin resin is as control:
Using two sections of calendering process, one section of mixing carbon black rubber master batch carries out in 1.5 L laboratory mixers, charging sequence: NR, carbon black
N550, white carbon black, TDAE, stearic acid, anti-aging agent RD, antioxidant 4020, tackifying resin, zinc oxide.Two-stage mixing adds vulcanization body
It ties up on 6 cun of open mills and carries out.Then plus accelerator NS, diphenylguanidine, insoluble sulfur one section of rubber master batch packet roller on a mill is taken,
Sulphur HDOT20 and DTDM, 3/4 cutting of left and right 2 times, minimum roll spacing is thin 4 times logical, and 2 mm roll spacing clots 4, bottom sheet is parked to be measured.
In above-mentioned sizing material, tackifying resin used is respectively embodiment, the resin of comparative example and Koresin resin, for each
The quality index of tackifying resin is as shown in table 2 below.
Note: heating loss refers to that by tackifying resin, ash content is that tackifying resin exists in 105 DEG C of heating 2h mass loss rates
550 ± 25 DEG C of 4 h of calcination are cooled to 200 DEG C or so, take out, and are put into drier cooling 30 min, calculate content of ashes.
As can be seen from Table 2, the tackifying resin of the embodiment of the present invention and comparative example is able to satisfy rubber thickening tree
The requirement of rouge heating loss≤1.0%, ash content≤0.5%, 120-150 DEG C of softening point, free phenol≤1%.Wherein, with comparative example
Product is compared, and the product colour of the embodiment of the present invention is deeper, this is because caused by the double bond structure in methacrylaldehyde.
Using the Mooney viscosity test machine GT-7080-S of high-speed rail instrument company production, according to GB/T 1233-2008 standard
The incipient scorch characteristic of rubber compound obtained by different tackifying resins is added in detection, as shown in table 3.
From 140 DEG C of mooney scorch experimental data t5 it can be seen that with not plus compared with the blank sample of tackifying resin, when in sizing material
After tackifying resin is added, time of scorch t5 shortens, and shortens amplitude about 20% or so.The time of scorch t5 of each sizing material connects
Closely, illustrate influence of the tackifying resin obtained by the present invention in terms of rubber compound incipient scorch characteristic to sizing material and alkyl phenolic resin in the market
Unanimously.
Each sizing material of above-mentioned gained is cut into the film of 180mm × 65mm, by film ordinary room temperature (20 DEG C, it is 50% opposite
Humidity) in the environment of store 1 day, 3 days, 5 days, 8 days, 15 days respectively, then take it is identical storage number of days two panels film, according to
The pressing speed of 20cm/min presses 5s, then avulses speed separation two panels film using 20 cm/min, test makes two panels glue
Power needed for piece separation, each storage number of days are repeated 5 times experiment under the same conditions, and taking its average value is the bonding force of sample,
Unit is newton (N).Laboratory apparatus is RZN-II rubber tack analyzer (one side Science and Technology Ltd. of Beijing all things on earth).
Sizing material self-adhesion implementations are characterized with the bonding force of each sizing material, bonding force shows that more greatly tack is better, as a result such as
Shown in table 4.
As shown in table 4, after each bin aging 1d, 3d, 5d, 8d, 15d, compared with the blank sizing material for not adding tackifying resin,
After tackifying resin is added, the tack of sizing material is significantly improved.Embodiment 1-6 is compared with comparative example 1-4, the tack of each sizing material
It is close, but in terms of persistent sticky, embodiment 1-6 and comparative example 1-4 show larger difference, tackifying resin tool of the present invention
There is better persistent sticky.Compared with Koresin resin, the initial viscosity of tackifying resin of the present invention is close with Koresin resin,
Persistent sticky is just slightly below Koresin resin, can be used as the substitute of Koresin resin.
Integrated application experimental result can be seen that the sample that various embodiments of the present invention obtain and the sample that comparative example obtains
Indices are qualified, and show similar performance in terms of rubber compound incipient scorch characteristic.But in application performances such as tacks
Aspect, product of the present invention and Koresin resin show higher persistent sticky.In addition, present invention process is simple to operation, right
Equipment requirement is low, cost of material is low and security performance is high, is suitble to industrialization promotion production.
Claims (10)
1. a kind of synthetic method of the modified p-tert-butylphenol acetaldehyde resin of methacrylaldehyde, it is characterized in that the following steps are included:
(1) p-tert-butylphenol and acetaldehyde are subjected to condensation reaction under the action of catalyst；
(2) after step (1), methacrylaldehyde is added into the product of step (1), continues condensation reaction under the action of catalyst；
(3) after step (2), reaction solution is adjusted to neutrality, organic solvent is added and extracts product, gained organic phase is distilled off organic
Solvent and water, then heating carries out polycondensation reaction, obtains the modified p-tert-butylphenol acetaldehyde resin of methacrylaldehyde.
2. synthetic method according to claim 1, it is characterized in that: the molar ratio of p-tert-butylphenol and acetaldehyde is 1.0:
0.8-0.9, preferably 1.0:0.85-0.9.
3. synthetic method according to claim 1 or 2, it is characterized in that: the quality of methacrylaldehyde is p-tert-butylphenol quality
5-10%.
4. synthetic method according to claim 1, it is characterized in that: the temperature of condensation reaction is 80 ~ 100 in step (1)
℃；In step (2), the temperature of condensation reaction is 80 ~ 100 DEG C；In step (3), the temperature of polycondensation reaction is 160 ~ 170
℃。
5. synthetic method according to claim 1 or 4, it is characterized in that: the time of condensation reaction is 1-3h in step (1)；
In step (2), the time of condensation reaction is 1-2h；In step (3), the time of polycondensation reaction is 0.5-2h.
6. synthetic method according to claim 1, it is characterized in that: in step (1) and (2), catalysis used in condensation reaction
Agent is acid, and the acid is organic acid or inorganic acid, the preferably concentrated sulfuric acid, oxalic acid or p-methyl benzenesulfonic acid.
7. synthetic method according to claim 1, it is characterized in that: water is first distilled off, adds propylene after step (1)
Aldehyde；In step (1) and (2), acetaldehyde instills in reaction system in form of an aqueous solutions, and reaction is added in the form being added dropwise in methacrylaldehyde
In system.
8. synthetic method according to claim 1, it is characterized in that: gained methacrylaldehyde is modified p-tert-butylphenol acetaldehyde resin
With structural formula described in following formula, in formula, R CH3Or CH=CH2, CH=CH2And CH3It exists simultaneously in following formula；
。
9. synthetic method according to claim 8, it is characterized in that: n=2-6.
10. synthetic method according to claim 1, it is characterized in that: the modified p-tert-butylphenol acetaldehyde resin of methacrylaldehyde
Weight average molecular weight is 800 ~ 1200, and softening point is 120-150 DEG C.
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| US3268467A (en) * | 1961-11-03 | 1966-08-23 | Goodyear Tire & Rubber | Adhesive composition comprising the reaction product of polyisocyanate and a formaldehyde condensate |
| US4032511A (en) * | 1975-03-03 | 1977-06-28 | Blount David H | Process for the production of phenol silicate compounds and their condensation products |
| CN101062971A (en) * | 2006-04-28 | 2007-10-31 | 中国科学院化学研究所 | Modified alkyd resin for laminated board and preparation method and usage thereof |
| CN102391449A (en) * | 2011-09-22 | 2012-03-28 | 华南理工大学 | Allyl para-tert-butyl phenyl ether formaldehyde tackifying resin and preparation method thereof |
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2018
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3268467A (en) * | 1961-11-03 | 1966-08-23 | Goodyear Tire & Rubber | Adhesive composition comprising the reaction product of polyisocyanate and a formaldehyde condensate |
| US4032511A (en) * | 1975-03-03 | 1977-06-28 | Blount David H | Process for the production of phenol silicate compounds and their condensation products |
| CN101062971A (en) * | 2006-04-28 | 2007-10-31 | 中国科学院化学研究所 | Modified alkyd resin for laminated board and preparation method and usage thereof |
| CN102391449A (en) * | 2011-09-22 | 2012-03-28 | 华南理工大学 | Allyl para-tert-butyl phenyl ether formaldehyde tackifying resin and preparation method thereof |
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