CN108503759A - A kind of synthetic method of alkyl phenolic resin - Google Patents
A kind of synthetic method of alkyl phenolic resin Download PDFInfo
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- CN108503759A CN108503759A CN201810196258.1A CN201810196258A CN108503759A CN 108503759 A CN108503759 A CN 108503759A CN 201810196258 A CN201810196258 A CN 201810196258A CN 108503759 A CN108503759 A CN 108503759A
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Abstract
The invention discloses a kind of alkyl phenolic resin and its synthetic methods, and the monosubstituted alkyl phenol of raw material and two substitution alkyl phenols are added in reactor, reacted with aldehyde under acidic catalyst effect, aldehyde is added after heating dehydration, alkyl phenolic resin is obtained by the reaction.Alkyl phenolic resin of the present invention has significantly more preferably Efficient Adhesive Promotion, and free phenol content reduction compared with similar alkyl phenolic resinoid.The invention also discloses application of the alkyl phenolic resin in tire and rubber product are manufactured.
Description
The application be submit on May 29th, 2014, application No. is 201410235452.8, it is entitled：A kind of " alkane
The divisional application of the Chinese invention patent application of the synthetic method of base phenolic resin ".
Invention field
The invention belongs to rubber manufacturing technology fields, and in particular to a kind of synthetic method of alkyl phenolic resin.
Technical background
Tackifying resin is the important compounding agent in rubber processing, is continuously increased with the usage amount of synthetic rubber, due to it
Tack is insufficient, and the importance of tackifying resin is being continuously increased.In tire industry, various different types of rubber components need
Can just embark on journey vulcanization after mutually fitting closely, so tackifying resin is essential in tire formulation.
The type of tackifying resin has hydrocarbon resins, rosin resin, alkyl phenolic resin and its modified product.Since thickening is imitated
Fruit is preferable, small on the influence of rubber mechanical property dynamic property, and Alkylphenolic Tackifying Resin becomes a kind of main technically classified rubber
Tackifying resin.Alkylphenolic Tackifying Resin mainly has octyl phenol, butyl phenol resin, generally alkylphenol-formaldehyde resin also to have few
Several classes are acetaldehyde, acetylene resin.Also a small number of products are modifiers on the basis of abovementioned alkyl fluosite.
Alkylphenolic Tackifying Resin is linear oligomer, and number-average molecular weight is generally between 500-1500, weight average molecular weight
2500 generally are not more than, because the extent of reaction of condensation reaction is low, more phenol is inevitably remained in resin
Class monomer, these free phenols can be brought into rubber product, and in rubber product in use, constantly being migrated from rubber product
Out, to pollute environment.The general method except free phenol mainly has：Washing, long-time vacuum, steam distillation etc.,
It is required for expending many working hours, the energy, or higher to equipment requirement, it is poor to implement difficulty, economic benefit.
The present invention relates to a kind of Alkylphenolic Tackifying Resin and preparation method thereof, the trip that has been simply and effectively reduced in resin
From phenol, the feature of environmental protection of product, and narrow molecular weight distribution are improved, compares common alkyl phenolic tackifying resins, Efficient Adhesive Promotion carries
It is high.
Invention content
In order to reduce the content for the alkyl phenol that dissociates in alkyl phenol phenolic tackifying resins, increase the feature of environmental protection of product, the present invention
Propose a kind of tackifying resin i.e. synthetic method of alkyl phenolic resin.Free phenol in the tackifying resin that the present invention synthesizes
Monomer is relatively low, and synthetic method is simple and convenient, reduces molecular weight distribution width, improves Efficient Adhesive Promotion.
The synthetic method of a kind of alkyl phenolic resin proposed by the present invention, by the monosubstituted alkyl phenol of raw material and two substitution alkyl
Phenol (for example, monosubstituted alkyl phenol and two total 1mol of substitution alkyl phenol) is by a certain percentage (for example, monosubstituted alkyl phenol and two substitutions
The molar ratio of alkyl phenol is 1:0.05~1) be added reactor in, under acidic catalyst effect, with a certain amount of aldehyde (for example,
The aldehyde of 0.5-1.2mol) it reacts at 70~180 DEG C, reach after target softening point (for example, 80-150 DEG C), then into one
Step removing residual moisture, it is completely rear to neutralize, obtain alkyl phenolic resin.Wherein, the molecular weight distribution of the alkyl phenolic resin
It is 1.4~1.8；The content of free alkyl phenol in the alkyl phenolic resin is 0.5%~3%.
In synthetic method of the present invention, it is R that the monosubstituted alkyl phenol, which is substituent group,1Monosubstituted alkyl phenol；Described two take
Substituted alkyl phenol is that substituent group is R2、R3、R4、R5Any one or two kinds two substitution alkyl phenols.
The reaction process of synthetic method of the present invention is as follows：
Wherein, R is hydrogen or methyl；R1For the naphthenic base or 6~18 of the alkyl of 1-18 carbon atom, 5~18 carbon atoms
The aryl of a carbon atom；R2、R3、R4、R5The alkyl of respectively 1-18 carbon atom, the naphthenic base of 5~18 carbon atoms or 6~
The aryl of 18 carbon atoms.Preferably, R is hydrogen or methyl；R1For the alkyl of 4-9 carbon atom；R2、R3、R4、R5Respectively 4-9
The alkyl of a carbon atom.
The product alkyl phenolic resin that the present invention synthesizes, wherein the content of the free alkyl phenol contained is 0.5%-3%.This
The molecular weight distribution for inventing the product alkyl phenolic resin of synthesis is 1.4-1.8.The product alkyl phenolic resin that the present invention synthesizes
Softening point be 80~150 DEG C.
In the product alkyl phenolic resin that the present invention synthesizes, including structure as shown below：
Wherein, R is hydrogen or methyl.R1For the naphthenic base or 6~18 of the alkyl of 1-18 carbon atom, 5~18 carbon atoms
The aryl of a carbon atom.Preferably, R1To be preferably the alkyl of 4-9 carbon atom.Preferably, R1For tertiary butyl or Te Xinji.
R2、R3、R4、R5The virtue of the alkyl of respectively 1-18 carbon atom, the naphthenic base of 5~18 carbon atoms or 6~18 carbon atoms
Base.R2、R3、R4、R5Group can be identical or different substituent group.Preferably, R2、R3、R4、R5Respectively 4-9 carbon atom
Alkyl.
In synthetic method of the present invention, the dosage molar ratio of the monosubstituted alkyl phenol of the raw material and two substitution alkyl phenols is 1:
0.05~1.Preferably, the dosage molar ratio 1 of monosubstituted alkyl phenol and two substitution alkyl phenols:0.05~0.5.
Wherein, it is R that the monosubstituted alkyl phenol of the raw material, which is substituent group,1Monosubstituted alkyl phenol.The monosubstituted alkane of raw material
Base phenol includes but not limited to p-methyl phenol, to normal-butyl phenol, p-tert-butylphenol, to tert-octylphenol, nonyl phenol, 12
It is one or more in alkyl phenol, octadecyl phenol.Preferably, the monosubstituted alkyl phenol of the raw material be p-tert-butylphenol, it is right
Tert-octylphenol, nonylphenol.
Wherein, it is R that the raw material two, which replaces alkyl phenol to be substituent group,2、R3、R4、R5Any one or two kinds two substitutions
Alkyl phenol.The raw material two replaces alkyl phenol to include but not limited to 2,4-DTBP, 2,6- DI-tert-butylphenol compounds, and 2,4-
Two tert-octylphenols, 2,6- bis- tert-octylphenols, 2,4- dioctyl phenol, 2- tertiary butyl -4- tert-octylphenols, 2- spy's octyl -
4-TBP, 2- tertiary butyl -4- octyl phenols are one or more in 2- octyls -4-TBP.
Wherein, the acidic catalyst be sulfuric acid, hydrochloric acid, benzene sulfonic acid or its alkyl substituents, phenol sulfuric acid or oxalic acid it
Any one or any two or more mixing.Preferably, the acidic catalyst is benzene sulfonic acid or its alkyl substituents, grass
Acid.
Wherein, the aldehyde is the one or both mixing of the formalin or paraformaldehyde of 10%~37% concentration, or
The one or both of acetaldehyde or para-acetaldehyde mixes.
The invention also provides a kind of alkyl phenolic resin being prepared according to the above-mentioned synthetic method, the product alkane
The content of free alkyl phenol in base phenolic resin is 0.5%-3%；Its molecular weight distribution is 1.4-1.8.
When preparing alkyl phenolic resin (dialkyl phenol-alkyl phenolic resin) using the method for the present invention, because of dialkyl phenol
Only there are one functional groups, can play the role of sealing end when connecting on phenolic resin strand, and the degree of polymerization is prevented to increase.Macromolecular is in chain
In propagation process, constantly there is monomer (including alkyl phenol and dialkyl phenol) to be connected on phenolic resin strand.From reaction probabilities
Consider, for initial reaction stage since alkyl phenol concentration is high, functional group is more, the mostly of formation are alkyl phenolic resins.With the extent of reaction plus
Deep, phenolic resin strand is longer, the probability nature higher blocked by dialkyl phenol, without how to undergo the trip of chain growth
It is relatively low from the probability that phenol and small molecule are blocked.In synthetic method of the present invention, in the conversion ratio higher reaction later stage, divide greatly
Son is mostly blocked, and cannot be further continued for chain growth, and it is more than use scope to avoid softening point.Add simultaneously into aldehyde, it is main and
Free alkyl phenol and small molecule are reacted so that the free alkyl phenol content in final product alkyl phenolic resin reduces.
Compared with commercially available alkylphenol formaldehyde tackifying resin, free phenol content is relatively low under same softening point, and product of the present invention is logical
It crosses after above-mentioned straightforward procedure synthesis, without last handling processes such as vacuum, washings, free phenol content i.e. reachable 1% is hereinafter, drop
Low energy consumption, working hour, monomer conversion are high, reduce the environmental pollution that last handling process is brought.The molecular weight of this product simultaneously
The more normal alkylphenol-formaldehyde resin of distribution is narrower, and the Efficient Adhesive Promotion of product is better than similar existing alkylphenol formaldehyde thickening tree
Fat.
It is existing with the trade mark, identical softening point alkylphenol-formaldehyde resin in, the low 1-3% of free phenol content contained,
Such as 118 DEG C -125 DEG C of para-tertiary butyl phenol formaldehyde resin of softening point, free phenol content in 3-4%, vacuum can most multipotency make to dissociate
Phenol is reduced to 2-3%.Compared with commercially available alkylphenol formaldehyde tackifying resin, product of the present invention is introduced by dialkyl phenol and is modified,
After being synthesized with straightforward procedure, it is not necessarily to the last handling processes such as vacuum, washing, the trip contained in product alkyl phenolic resin of the present invention
From phenol content i.e. reachable 1% hereinafter, reducing energy consumption, working hour, monomer conversion height, reduce the ring that last handling process is brought
It pollutes in border.Moreover, the more existing alkylphenol-formaldehyde resin of the molecular weight distribution of product of the present invention is narrower, according to dialkyl phenol dosage
Difference, molecular weight distributing index PDI is in 1.4-1.9, and existing alkylphenol-formaldehyde resin molecular weight distributing index generally exists
1.8-2.2。
The notable excellent Efficient Adhesive Promotion of alkyl phenolic resin tool that the present invention synthesizes.The present invention passes through in resin synthesis process
The disubstituted alkyl phenol in middle addition part, effectively reduces the free phenol content in phenolic resin, improves the feature of environmental protection of product.
The reason of free phenol in product alkyl phenolic resin of the present invention significantly reduces is the introducing of dialkyl phenol.Alkyl
Phenol and formaldehyde are all the monomers of two functional groups, and the conversion ratio of alkyl phenol must just be improved by reducing free phenol, but higher conversion
Rate can bring excessively high molecular weight and softening point so that resin can not use.According to condensation reaction theory, molecular weightReaction
There is following relationship between degree P, equivalent coefficient γ：
The type and resin softening point of alkyl phenol require the magnitude range of the molecular weight of limitation.Molecular weightCertain feelings
Under condition, extent of reaction P, equivalent coefficient γ are related.
It introduces after monofunctional dialkyl phenol, equivalent coefficient γ is reduced, and extent of reaction P then increases so that resin
Middle free phenol is reduced.
There is preferable Efficient Adhesive Promotion when tackifying resin is in certain molecular weight ranges.When molecular weight is too small, alkane
Anchoring effect of one section of the base in rubber is inadequate；When molecular weight is excessive, the migration energy force difference in resin cannot be in rubber interface
Enough orientations are formed to obtain Efficient Adhesive Promotion by hydrogen bond.The alkyl phenolic resin synthesized using preparation method of the present invention
(dialkyl phenol-Alkylphenolic Tackifying Resin) is acted on using the sealing end of dialkyl phenol, and long-chain molecule is in propagation process, quilt
Probability higher is blocked, to reduce macromolecular weight, macromolecular proportion of the chain number more than 10 is decreased obviously.And
When second segment adds aldehyde reaction, monomer conversion has been raised so that it is low to contain only 2-3 chain link for resin small molecular content
Polymers reduces.Molecular weight distribution concentrates on one compared in zone of reasonableness, i.e., shared by the phenolic resin molecule containing 6-9 chain link
Ratio increases, so product of the present invention is made to be improved compared to the performance of existing alkyl phenol tackifying resin.
Application the present invention also provides the alkyl phenolic resin of synthesis in rubber product manufacture as tackifier, and its
Application in tire material glue as tackifier.The alkyl phenolic resin that the present invention synthesizes is applied to rubber composition, enhances
The tack of rubber, compared with prior art in similar product, thickening property is improved, and the alkyl phenol that the present invention synthesizes
Free phenol content in urea formaldehyde product is very low, and product has the apparent feature of environmental protection.Compared with other method of modifying, in benzaldehyde product
Other modified materials are not introduced, structure is approximate with existing alkylphenol-formaldehyde resin, will not be generated to rubber performance other unknown
It influences, especially suitable for being applied in tyre stock.
Specific implementation mode
In conjunction with following specific examples, invention is further described in detail, the present invention protect content be not limited to
Lower embodiment.Without departing from the spirit and scope of the invention, various changes and advantages that will be apparent to those skilled in the art are all
It is included in the present invention, and using appended claims as protection domain.
Reference Example 1
On tetra- neck reaction bulbs of 1000ml, installation stirring, thermometer, reflux condenser.Put into p-tert-butylphenol
300g, 37% formalin 105g, p- toluenesulfonic acid 1.0g.Solvent toluene 20g is warming up to 100 DEG C.Next time at 100 DEG C
Stream reaction 2 hours.Normal pressure is warming up to 190 DEG C of piptonychia benzene and water, and the aqueous solution of 0.7g sodium hydroxides 20% is added to neutralize.It is warming up to
200 DEG C, and keep the temperature 2 hours at this temperature.Resin melt is discharged into stainless steel disc, is cooled to room temperature.Product is transparent, softening point
127 DEG C, crocus, structure is：
Its free phenol, molecular weight, molecular weight distribution data are shown in Table 2.
Reference Example 2
On tetra- neck reaction bulbs of 1000ml, installation stirring, thermometer, reflux condensing tube and addition funnel.It is pungent to put into p- spy
Dodecyl benzene sulfonic acid 2g is added in base phenol 412g, 37% formalin 80g.100 DEG C are warming up to, is flowed back at 100 DEG C anti-
It answers 2 hours.Normal pressure is dehydrated.It waits for that temperature rises to 140 DEG C, gradually adds solid aldehyde 11g.It is warming up to 160 DEG C and takes off residual water, add 1.1g hydrogen-oxygens
The aqueous solution for changing sodium 20% neutralizes, and keeps the temperature 2 hours at this temperature.Resin melt is discharged into stainless steel disc, is cooled to room temperature.Production
Product are transparent, 94 DEG C of softening point, brown color.
Its free phenol, molecular weight, molecular weight distribution data are shown in Table 3.
Embodiment 1
On tetra- neck reaction bulbs of 1000ml, installation stirring, thermometer, reflux condensing tube and addition funnel.Put into p- tertiary fourth
Base phenol 285g, 2,4-DTBP 20.6g, p- toluenesulfonic acid 1.0g, solvent toluene 20g, 37% formalin
110g is warming up to 100 DEG C, back flow reaction 2 hours.Normal pressure is warming up to 190 DEG C of dehydrations and toluene, adds 0.7g sodium hydroxides 20%
Aqueous solution neutralizes.200 DEG C are warming up to, and keeps the temperature 2 hours at this temperature.Resin melt is discharged into stainless steel disc, is cooled to room temperature.
Product crocus, 126 DEG C of softening point.Molecular resin amount is larger when dehydration, is added when solvent toluene is to reduce dehydration and reacts
The viscosity of system.
Embodiment 2
On tetra- neck reaction bulbs of 1000ml, installation stirring, thermometer, reflux condensing tube and addition funnel.Put into p- tertiary fourth
Base phenol 255g, 2,4-DTBP 61.8g, p- toluenesulfonic acid 1.2g, 37% formalin 90g are warming up to
100 DEG C, back flow reaction 2 hours.Normal pressure is warming up to 140 DEG C of dehydrations, then gradually adds solid aldehyde 16g, be warming up to 190 DEG C it is de- residual
Water adds the aqueous solution of 0.8g sodium hydroxides 20% to neutralize.200 DEG C are warming up to, and keeps the temperature 2 hours at this temperature.Resin is melted
Body is discharged into stainless steel disc, is cooled to room temperature.Product crocus, 127 DEG C of softening point.
Embodiment 3
On tetra- neck reaction bulbs of 1000ml, installation stirring, thermometer, reflux condensing tube and addition funnel.Put into p- tertiary fourth
Base phenol 180g, 2,4-DTBP 164.8g, p- toluenesulfonic acid 1.2g, solvent toluene 20g, 37% formaldehyde are water-soluble
Liquid 120g is warming up to 100 DEG C, back flow reaction 2 hours.Normal pressure temperature rises to 190 DEG C of dehydrations and toluene, adds 0.8g sodium hydroxides
20% aqueous solution neutralizes.200 DEG C are warming up to, and keeps the temperature 2 hours at this temperature.Resin melt is discharged into stainless steel disc, it is cold
To room temperature.Product crocus, 125 DEG C of softening point.
Embodiment 4
On tetra- neck reaction bulbs of 1000ml, installation stirring, thermometer, reflux condensing tube and addition funnel.Put into p- tertiary fourth
Base phenol 150g, 2,4-DTBP 206g, p- toluenesulfonic acid 1.2g, 37% formalin 90g are warming up to 100
DEG C, back flow reaction 2 hours.Normal pressure is dehydrated.Temperature rises to 140 DEG C, then gradually adds solid aldehyde 22g, be warming up to 190 DEG C it is de- residual
Water adds the aqueous solution of 0.8g sodium hydroxides 20% to neutralize.200 DEG C are warming up to, and keeps the temperature 2 hours at this temperature.Resin is melted
Body is discharged into stainless steel disc, is cooled to room temperature.Product crocus, 120 DEG C of softening point.
Embodiment 5
On tetra- neck reaction bulbs of 1000ml, installation stirring, thermometer, reflux condensing tube and addition funnel.It is pungent to put into p- spy
Base phenol 370.8g, 2,4- bis- tert-octylphenol 63.6g, p-methyl benzenesulfonic acid 0.8g, oxalic acid 1g, 37% formalin 85g,
100 DEG C are warming up to, back flow reaction 2 hours at 100 DEG C.Normal pressure is dehydrated.It waits for that temperature rises to 140 DEG C, gradually adds solid aldehyde 12g.
It is warming up to 160 DEG C and takes off residual water, the aqueous solution of 1.2g sodium hydroxides 20% is added to neutralize, and keep the temperature 2 hours at this temperature.By resin
Melt is discharged into stainless steel disc, is cooled to room temperature.Product is transparent, 95 DEG C of softening point, brown color.
Embodiment 6
On tetra- neck reaction bulbs of 1000ml, installation stirring, thermometer, reflux condensing tube and addition funnel.It is pungent to put into p- spy
Base phenol 309g, 2,4- bis- tert-octylphenol 159g, dodecyl benzene sulfonic acid 1.6g, 37% formalin 85g are warming up to
100 DEG C, back flow reaction 2 hours at 100 DEG C.Normal pressure is dehydrated.It waits for that temperature rises to 140 DEG C, gradually adds solid aldehyde 15g.It is warming up to
160 DEG C take off residual water, and the aqueous solution of 1.2g sodium hydroxides 20% is added to neutralize, and keep the temperature 2 hours at this temperature.Resin melt is arranged
Enter stainless steel disc, is cooled to room temperature.Product is transparent, 96 DEG C of softening point, brown color.
Embodiment 7
Catalyst is made with cation exchange resin, with excessive diisobutylene alkanisation phenol, alkylation liquid is obtained, analyzes alkylation liquid
Composition：Have to tert-octylphenol 43%, p-tert-butylphenol 7%, 2, bis- tert-octylphenols 38% of 4-, 2- tertiary butyl -4- spies are pungent
Base phenol 12%, alkyl phenol and dialkyl phenol molar ratio are about 0.6 in alkylation liquid:0.4, on tetra- neck reaction bulbs of 1000ml, peace
Fill stirring, thermometer, reflux condensing tube and addition funnel.Above-mentioned alkanisation liquid mixture 400g, p-methyl benzenesulfonic acid 0.8g are put into,
Oxalic acid 1g, 37% formalin 91g are warming up to 100 DEG C, back flow reaction 2 hours at 100 DEG C.Normal pressure is dehydrated.Wait for temperature liter
To 140 DEG C, solid aldehyde 19g is gradually added.It is warming up to 160 DEG C and takes off residual water, the aqueous solution of 1.2g sodium hydroxides 20% is added to neutralize, and
2 hours are kept the temperature at a temperature of this.Resin melt is discharged into stainless steel disc, is cooled to room temperature.Product is transparent, 95 DEG C of softening point, brown color.
Embodiment 8
Catalyst is made with cation exchange resin, with excessive octene alkanisation phenol, alkylation liquid is obtained, analyzes alkylation liquid group
At：There are p-Octylphenol 68%, 4- butylphenols 4%, 2,4- dioctyl phenol 23%, 2- butyl -6- octyl phenols 5%, alkane
Base phenol and dialkyl phenol molar ratio are about 0.8:0.2.On tetra- neck reaction bulbs of 1000ml, installation stirring, thermometer, reflux condensation mode
Pipe and addition funnel.Put into above-mentioned alkanisation liquid mixture 400g, p-methyl benzenesulfonic acid 0.8g, oxalic acid 1g, 37% formalin
90g is warming up to 100 DEG C, back flow reaction 2 hours at 100 DEG C.Normal pressure is dehydrated.It waits for that temperature rises to 140 DEG C, gradually adds solid aldehyde
14g.It is warming up to 160 DEG C and takes off residual water, the aqueous solution of 1.2g sodium hydroxides 20% is added to neutralize, and keep the temperature 2 hours at this temperature.It will
Resin melt is discharged into stainless steel disc, is cooled to room temperature.Product is transparent, 94 DEG C of softening point, brown color.
Embodiment 9
Catalyst is made with cation exchange resin, with excessive nonene, octene alkanisation phenol, alkylation liquid is obtained, analyzes alkanisation
Liquid forms：There are p-Octylphenol 36%, n nonylphenol 28%, 4- butylphenols 3%, 4- amyl phenols 2%, 2,6- dioctyl benzene
Phenol 18%, 2,4- dinonyl phenols 11%, 2- butyl -4- octyl phenols 2%, alkyl phenol are about with dialkyl phenol molar ratio
0.78:0.22.On tetra- neck reaction bulbs of 1000ml, installation stirring, thermometer, reflux condensing tube and addition funnel.It puts into above-mentioned
Alkanisation liquid mixture 400g, p-methyl benzenesulfonic acid 0.8g, oxalic acid 1g, 37% formalin 83g are warming up to 100 DEG C, 100
Back flow reaction 2 hours at DEG C.Normal pressure is dehydrated.It waits for that temperature rises to 140 DEG C, gradually adds solid aldehyde 17g.It is warming up to 160 DEG C and takes off residual water,
Add the aqueous solution of 1.2g sodium hydroxides 20% to neutralize, and keeps the temperature 2 hours at this temperature.Resin melt is discharged into stainless steel disc,
It is cooled to room temperature.Product is transparent, 92 DEG C of softening point, brown color.
Embodiment 10 detects resin viscosity
Resin viscosity detection method is as follows：
The first step is kneaded butadiene rubber, natural rubber, carbon black, operation oil, stearic acid in mixer in 150 DEG C or so
And zinc oxide, obtain masterbatch；Second step, the product being separately added into a certain amount of masterbatch in Reference Example and implementation
Product tackifying resin in example, additionally incorporates anti-aging agent TMQ and 4020, and be kneaded in mixer in 140 DEG C or so；Third
It walks, Sulfur and accelerator NS is added in the sizing material obtained to second step, be kneaded on a mill, tabletting, obtain film for rubber.It will
These films are stored under conditions of 23 DEG C, 50% humidity, and 24 hours, 48 hours and 72 hours self-adhesions are stored in test respectively
Property.The Japanese Toyo Seiki company P-2 type adhesiveness testers detection of tack.
Following table 1 indicates Rubber mix formulations.The Product formation resin alkyl being prepared in the above various embodiments 1-9
The characterization of phenolic resin is shown in Table 2-4.It is shown in Table 5 using the tack testing result of the film for rubber of different tackifying resins.
The formula of film for rubber in the detection of 1 resin viscosity of table
| Serial number | Raw material | Formula |
| 1 | Natural rubber | 30.0 |
| 2 | Butadiene rubber | 70.0 |
| 3 | Carbon black N375 | 80.0 |
| 4 | Oil | 4.0 |
| 5 | Stearic acid | 2.0 |
| 6 | Zinc oxide | 3.0 |
| 7 | Sulphur (80%) (OT20) | 1.0 |
| 8 | Product obtained in product or embodiment 1-9 obtained in Reference Example 1 or 2 | 4.0 |
| 9 | Sulfenamide NS | 2.2 |
| 10 | Anti-aging agent TMQ | 1.5 |
| 11 | Antioxidant 4020 | 1.6 |
2 resin testing result of table
3 resin testing result of table
| Content (%) | Reference Example 2 | Embodiment 5 | Embodiment 6 |
| Free Ptop | 2.8% | 2.0% | 1.4% |
| Bis- special octyl phenols of free 2,4- | 0 | 0.1% | 0.2% |
| Molecular weight distributing index PDI | 2.2 | 1.8 | 1.7 |
| Number-average molecular weight Mn | 1036 | 1195 | 1260 |
4 resin testing result of table
| Content (%) | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| Dissociate to octyl phenol | 0.7% | 1.4% | 1.1% |
| Dissociate to butylphenol | 0.1% | 0.1% | 0.1% |
| Free n nonylphenol | 0 | 0 | 0.8% |
| Total free dialkyl phenol | 0.5% | 0.2% | 0.2% |
| Molecular weight distributing index PDI | 1.6 | 1.7 | 1.8 |
| Number-average molecular weight Mn | 1320 | 1247 | 1154 |
5 rubber applications of table test thickening property result
Table 2 illustrates compared with existing p-tert-butylphenol (PTBP)-formaldehyde tackifying resin, total by PTBP and dialkyl phenol
Poly- to be modified, free phenol content reduces in resin, while as dialkyl phenol dosage increases, molecular weight distribution sharp.
The explanation of table 3 with it is existing to tert-octylphenol (PTOP)-formaldehyde tackifying resin compared with, be total to by PTOP and dialkyl phenol
Poly- to be modified, free phenol content reduces in resin, while as dialkyl phenol dosage increases, molecular weight distribution sharp.
Table 4 illustrates that other type alkylphenol-formaldehyde resins can also use dialkyl phenol modification by copolymerization, and it is identical to reach the present invention
Effect, two substitution alkyl phenols include but not limited to 2,4-DTBP, 2,6- DI-tert-butylphenol compounds, 2,4- bis- special octyl benzene
Phenol, 2,6- bis- tert-octylphenols, 2,4- dioctyl phenol, 2- tertiary butyl -4- tert-octylphenols, 2- spy's octyl -4- tert-butyl benzenes
Phenol, 2- tertiary butyl -4- octyl phenols are one or more in 2- octyls -4-TBP.
Table 5 illustrate this product synthesis resin on Efficient Adhesive Promotion more than existing alkylphenol-formaldehyde resin product Efficient Adhesive Promotion
It is good.
The above result shows that the present invention can be reduced effectively using dialkyl phenol and alkyl phenol copolymerization tackifying resin
Free phenol content in naval stores improves the feature of environmental protection of product, while the sealing end effect of dialkyl phenol reduces point of resin
Son amount distribution so that most molecular weight is able to concentrate in a preferred range in resin macromolecule, and molecular weight is moderate,
To improve the viscosity performance of resin.
Claims (10)
1. a kind of synthetic method of alkyl phenolic resin, which is characterized in that being added raw material monoalkyl phenol and dialkyl phenol to anti-
Device is answered, under acidic catalyst effect, is reacted at 70~180 DEG C with aldehyde, after the reaction was complete, removes moisture content, neutralization obtains
The dosage molar ratio of the alkyl phenolic resin, the monoalkyl phenol and dialkyl phenol is 3：2-1：1.
2. synthetic method as described in claim 1, which is characterized in that the monoalkyl phenol is p-tert-butylphenol；Described two
Alkyl phenol is 2,4- DI-tert-butylphenol compounds or 2,6 di t butyl phenol.
3. synthetic method as described in claim 1, which is characterized in that the molecular weight distribution of the alkyl phenolic resin is 1.4
~1.8；The content of free alkyl phenol in the alkyl phenolic resin is 0.5%~3%.
4. synthetic method as described in claim 1, which is characterized in that it is R that the monoalkyl phenol, which is substituent group,1Monoalkyl phenol；
The dialkyl phenol is that substituent group is R2、R3、R4、R5Any one or two kinds dialkyl phenol；The reaction of the synthetic method
Process is as follows：
Wherein, R is hydrogen or methyl；R1For the naphthenic base or 6~18 carbon originals of the alkyl of 1-18 carbon atom, 5~18 carbon atoms
The aryl of son；R2、R3、R4、R5The naphthenic base or 6~18 carbon of the alkyl of respectively 1-18 carbon atom, 5~18 carbon atoms
The aryl of atom.
5. synthetic method as described in claim 1, which is characterized in that the monoalkyl phenol is p-methyl phenol, to normal-butyl
Phenol, p-tert-butylphenol, to one or more in tert-octylphenol, nonyl phenol, dodecylphenol, octadecyl phenol.
6. synthetic method as described in claim 1, which is characterized in that the raw material dialkyl phenol is 2,4- di-tert-butyls
Phenol, 2,6- DI-tert-butylphenol compounds, 2,4- bis- tert-octylphenols, 2,6- bis- tert-octylphenols, 2,4- dioctyl phenol, the tertiary fourths of 2-
Base -4- tert-octylphenols, 2- spy's octyl -4-TBP, 2- tertiary butyl -4- octyl phenols, 2- octyls -4-TBP
In it is one or more.
7. synthetic method as described in claim 1, which is characterized in that the acidic catalyst be sulfuric acid, hydrochloric acid, benzene sulfonic acid or
Any one or any two or more mixing of its alkyl substituents, phenol sulfuric acid or oxalic acid；The aldehyde is 10%~37%
The one or both mixing or the mixing of the one or both of acetaldehyde or para-acetaldehyde of the formalin or paraformaldehyde of concentration.
8. a kind of synthetic method of alkyl phenolic resin, which is characterized in that the method is：It is catalyzed with cation exchange resin
Agent obtains alkylation liquid, analysis alkylation liquid composition with excessive nonene, octene alkanisation phenol：There is p-Octylphenol 36%, to nonyl
Phenol 28%, 4- butylphenols 3%, 4- amyl phenols 2%, 2,6- dioctyl phenol 18%, 2,4- dinonyl phenols 11%, 2- fourths
Base -4- octyl phenols 2%, alkyl phenol and dialkyl phenol molar ratio are about 0.78:0.22, on tetra- neck reaction bulbs of 1000ml, peace
Stirring, thermometer, reflux condensing tube and addition funnel are filled, above-mentioned alkanisation liquid mixture 400g, p-methyl benzenesulfonic acid 0.8g are put into,
Oxalic acid 1g, 37% formalin 83g are warming up to 100 DEG C, back flow reaction 2 hours at 100 DEG C, and normal pressure dehydration waits for temperature liter
To 140 DEG C, solid aldehyde 17g is gradually added, 160 DEG C is warming up to and takes off residual water, the aqueous solution of 1.2g sodium hydroxides 20% is added to neutralize, and
2 hours are kept the temperature at a temperature of this, resin melt is discharged into stainless steel disc, is cooled to room temperature, product is transparent, 92 DEG C of softening point, brown color.
9. the alkyl phenolic resin that a kind of any one the method such as claim 1 to 8 is prepared.
10. alkyl phenolic resin as claimed in claim 9 plays answering for tackifying effect in rubber product manufacture as tackifier
With.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109810231A (en) * | 2019-01-24 | 2019-05-28 | 山东阳谷华泰化工股份有限公司 | A kind of 4- di-t-alkylphenol-(phenylol) formaldehyde resin and its preparation method and application |
| CN114316227A (en) * | 2022-01-11 | 2022-04-12 | 安徽智成实业有限公司 | Polyester resin with excellent yellowing resistance for powder coating and preparation method thereof |
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| BE1023496B1 (en) * | 2016-03-09 | 2017-04-07 | Sumitomo Bakelite Europe N.V. | Process for the preparation of NOVOLAK ALKYLPHENOL RESINS |
| CN106967204B (en) * | 2016-03-28 | 2020-03-31 | 华奇（中国）化工有限公司 | Synthesis and application of long-acting tackifying phenolic resin |
| CN108329444B (en) * | 2018-01-31 | 2020-04-28 | 山东阳谷华泰化工股份有限公司 | Solid acid catalytic synthesis method of tackifying alkyl phenolic resin |
| CN109456454B (en) * | 2018-08-23 | 2021-07-09 | 彤程化学（中国）有限公司 | Low-phenol alkylphenol-formaldehyde resin and preparation method and application thereof |
| CN109880031B (en) * | 2018-12-07 | 2021-11-02 | 山东阳谷华泰化工股份有限公司 | Preparation method of mixed alkylphenol-formaldehyde resin rubber tackifier |
| KR20230022064A (en) * | 2021-08-06 | 2023-02-14 | 코오롱인더스트리 주식회사 | A process of preparing the alkyl phenolic resin, an alkyl phenolic resin, and a rubber composition including the same |
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| CN114316227A (en) * | 2022-01-11 | 2022-04-12 | 安徽智成实业有限公司 | Polyester resin with excellent yellowing resistance for powder coating and preparation method thereof |
| CN114316227B (en) * | 2022-01-11 | 2023-09-05 | 安徽智成实业有限公司 | Polyester resin with excellent yellowing resistance for powder coating and preparation method thereof |
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| CN104031220B (en) | 2018-04-24 |
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| CN104031220A (en) | 2014-09-10 |
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