CN106608956B - A kind of preparation method and application of alkyl phenol-phenol-formaldehyde resin - Google Patents
A kind of preparation method and application of alkyl phenol-phenol-formaldehyde resin Download PDFInfo
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Abstract
The present invention proposes a kind of preparation method of alkyl phenol-phenol-formaldehyde resin, and contraposition substitution alkyl phenol is reacted with first segment aldehyde under the conditions of basic catalyst first, generates hydroxymethyl alkyl phenol；Then acidic catalyst and phenol are added into mixture so that methylol and phenol reactant；It is eventually adding second segment aldehyde to be reacted, alkyl phenol-phenol-formaldehyde resin of the modified by alkyl phenol is obtained after dehydration.The content of free phenol is greatly reduced in alkyl phenol-phenol-formaldehyde resin obtained by the present invention, and with the comparable thickening property of resorcinol class binder resin, salt water resistance ageing properties and steam ageing-resistant performance that steel wire covers glue can be improved.Product obtained by the method for the present invention can cover glue, tire body cord, tyre surface or rubber cover as rubber adhesion accelerating agent applied to steel wire.
Description
Technical field
The present invention relates to rubber resin manufacture fields, and in particular to a kind of preparation method of alkyl phenol-phenol-formaldehyde resin
And its application as rubber adhesion accelerating agent.
Background technology
In the production of reinforced rubber product such as tire and hose, usually use staple fibre, nylon, polyester, steel wire and
Each framework material such as glass fibre is used for increasing the intensity of rubber product.Bonding can be used usually between framework material and rubber
System, for example, binder resin (methylene acceptor).More use resorcinol as methylene acceptor in the prior art, with
Hexa (HMT) and hexamethoxymethyl melamine (HMMM) are used as methylene donor compound, to promote steel
The bonding of cord and rubber/rubber composition.In sulfuration process, methylene donor releases formaldehyde, formaldehyde and isophthalic two
Phenol reaction in-situ forms resorcinol-formaldehyde (RF) network structure, and the object of vulcanized rubber can be improved by being formed by network structure
Rationality energy, mechanical performance and bond properties, and after forming adhesive layer good connection is played with sizing material and steel wire adhesive layer
And transitional function.
In the prior art often using resorcinol monomer as methylene acceptor jointing material, but due to the smoke of resorcinol
Point it is relatively low, (150 DEG C~200 DEG C) release the harmful substance for endangering health in mixing process, therefore, just gradually by
The resorcinol-formaldehyde resin of preshrunk sum is replaced.Further occur the resorcinol-formaldehyde resin of alkanisation modification again,
They have lower free resorcinol content (1-5%).
Phenol is the same with resorcinol, and also there are three degrees of functionality, and phenol formaldehyde resin is with methylene donor with the use of same
Sample can form the connection that cross-linked network promotes and protect framework material and rubber.Wheel for curing temperature at 150 DEG C or more
For tire product, high temperature makes phenol and methylene donor also have reaction speed quickly, resorcinol can be replaced quick
Phenol-formaldehyde (PF) network structure is formed, the physical property, mechanical performance and bond properties of vulcanized rubber are improved.Phenol simultaneously
Boiling point is relatively low, is easy to obtain low-free phenol product by vacuum industry in industrial production.It can be further with alkyl phenol copolymerization
Free phenol is reduced, is used as rubber adhesion accelerating agent, the target of production green rubber product may be implemented.
There are many hydroxyls in resorcinol formaldehyde resin, water imbibition is stronger, is added in rubber as rubber adhesion accelerating agent
In use, wet and heat ageing resistant and salt water resistance the ageing properties performance of rubber are poor.
Invention content
To overcome the deficiencies of existing technologies, the present invention proposes a kind of preparation method of alkyl phenol-phenol-formaldehyde, made
Water imbibition substantially reduces standby resin compared with prior art, and can improve rubber product as adhesion promotor invades moisture content
Lead to the resistivity of aging.
Alkalinity and acid two kinds of catalyst are successively used in preparation method of the present invention, and it is competing poly- relative to phenol to overcome alkyl phenol
The problem of rate is low, and copolymerization is easy to form block structure so that the alkyl phenol of low activity obtains higher conversion ratio, with phenol one
It rises and forms more uniform copolymeric structure, improve dispersion performance of the resin in rubber and anti-with methylene donor
It should be able to power.The physical property, mechanical performance and bond properties of vulcanized rubber can preferably be improved in rubber by applying.
The present invention proposes a kind of preparation method of alkyl phenol-phenol-formaldehyde resin, the alkyl phenol-phenol-formaldehyde tree
Fat is the rubber adhesion accelerating agent of modified by alkyl phenol, and the preparation method comprises the following steps：By alkyl phenol, organic solvent and alkali
Property catalyst be added reactor in, be added first segment aldehyde, carried out under the conditions of 70 DEG C~90 DEG C reaction 1-3 hours；Phenol is added,
Acidic catalyst is added, is warming up to 100 DEG C；Second segment aldehyde is added, reaction heats up after 1-4 hours and is dehydrated, and obtains the alkyl
Phenol-phenol-formaldehyde resin.
The preparation method specifically includes three steps：
The first step：Alkyl phenol is under the conditions of basic catalyst and first segment aldehyde reaction generates hydroxymethyl alkyl phenol, middle part
Point hydroxymethyl alkyl phenol can be condensed as dimer, shown in reaction process such as formula (I):
I.e.：
Or
The molar ratio of the wherein described alkyl phenol and first segment aldehyde is 1:2-2.5.Preferably, alkyl phenol and first segment aldehyde rub
You are than being 1:2-2.1.Because alkyl phenol is only there are two degree of functionality, under conditions of aldehyde phenol ratio >=2, it is ensured that alkyl phenol is abundant
Reaction, reaches higher conversion ratio so that the content for the alkyl phenol that dissociates in the resin finally obtained is relatively low (< 1%).Relatively low
Temperature (70 DEG C~90 DEG C) and alkaline condition under, methylol is more stable, and hydroxymethyl alkyl phenol autohemagglutination is slower, there is the sufficient time
Phenol addition can be waited for be copolymerized, obtain homogeneous copolymer.
Second step：Hydroxymethyl alkyl phenol is reacted with phenol under conditions of acidic catalyst, reaction process such as formula
(II) shown in：
I.e.：
Or
It is added in super acid catalyst and after base catalyst, system PH becomes acid from alkalinity, and methylol faces position with phenol
Reactive hydrogen, which reacts rapidly, generates methylene bridged bond, and the ehter bond among alkyl phenol dimer also releases formaldehyde, becomes methylene.
Third walks：Continue under the conditions of acidic catalyst and second segment aldehyde reaction obtains the target resin i.e. alkyl phenol-
Phenol-formaldehyde resin, shown in reaction process such as formula (III)：
I.e.：
Or
Wherein, the molar ratio of alkyl phenol and phenol described in the preparation method is 0.05-0.3:1, it is preferable that the alkane
The molar ratio of base phenol and phenol is 0.08-0.15:1.Phenolic resin is polar molecule, and the alkyl phenol of addition carries out modification by copolymerization,
The compatibility of resin and rubber can be improved, excessive, then active site reduction in resin is added, giving precursor reactant with methylene becomes
Slowly, finally formed phenol-formaldehyde (PF) network density reduces.So the molar ratio of suitable alkyl phenol and phenol is 0.05-
0.3:1, it is preferably in a proportion of 0.08-0.15:1.
Basic catalyst described in the preparation method is ammonium hydroxide, alkylamine, dialkylamine, trialkylamine, six methines
Tetramine diethanol amine triethanolamine alkali metal, alkaline earth oxide, hydroxide it is any one or any two or more
Combination.
Acidic catalyst described in the preparation method is times of sulfuric acid, benzene sulfonic acid and its alkyl substituents, phenol sulfuric acid
It anticipates a kind of or arbitrary two or more combination.
Aldehyde described in the preparation method be the formalin of 10%~37% concentration, paraformaldehyde any one or
Two kinds of combination.
The invention also provides a kind of alkyl phenol-phenol-formaldehyde resins, are obtained by the preparation method of the present invention, the tree
Shown in fat structure such as formula (a)：
Wherein, R is the alkyl of C4-C20；
N=1 or 2；
M, o are positive integers.
Wherein, the softening point of the alkyl phenol-phenol-formaldehyde resin is 90 DEG C~120 DEG C.Wherein, the resin middle reaches
Content from phenol is the 0.5%-2% of resin quality；The content of free alkyl phenol is the 0-1% of resin quality.
The invention also provides be applied to steel wire using the alkyl phenol-phenol-formaldehyde resin as rubber adhesion accelerating agent
Cover glue, tire body cord, the application of tyre surface or rubber cover.
The beneficial effects of the present invention are be added the alkyl phenol-phenol-formaldehyde resin as rubber adhesion accelerating agent
When in rubber, it can obtain and the comparable Efficient Adhesive Promotion of resorcinol class binder resin.Simultaneously as the hydroxyl in resin is reduced
, compared with resorcinol resinoid, when alkyl phenol-phenol-formaldehyde resin prepared by the present invention is applied to rubber, can make
Rubber wet and heat ageing resistant and salt water resistance ageing properties be improved significantly.
Description of the drawings
Fig. 1 is the gpc chromatogram for the product that embodiment 5 is prepared.
Specific implementation mode
In conjunction with following specific examples, the present invention is described in further detail.Implement the present invention process, condition,
Experimental method etc. is among the general principles and common general knowledge in the art, the present invention does not have in addition to the following content specially referred to
Especially limitation content.The protection content of the present invention is not limited to following embodiment.In the spirit and scope without departing substantially from inventive concept
Under, various changes and advantages that will be apparent to those skilled in the art are all included in the present invention, and with the attached claims
Book is protection domain.
The present invention experiment in, phenol, p-tert-butylphenol (PTBP), to tert-octylphenol (PTOP), to dodecylphenol
(PDDP) it is technical grade.Formaldehyde is technical grade, concentration 36.7-37.1%.Gu aldehyde is technical grade, content of formaldehyde 92-95%.
Gu aldehyde, that is, paraformaldehyde (CH2O) n, molecular weight 30n, structural formula are：
N is the degree of polymerization, is industrially commonly used to substitute liquid aldehyde to improve aldehyde concentration, improves reaction efficiency, and reduce waste water.It is poly-
Right n more low reaction when depolymerization it is faster, reaction it is more violent.In resin synthesis process, paraformaldehyde (CH2O) n can be decomposed completely
Reaction is participated in for n CH2O of formaldehyde, front and back mass conservation is decomposed, eventually becomes methylene and enter in resin structure, implement below
Solid aldehyde mole is practical in example is finally decomposed to formaldehyde CH for solid aldehyde2The mole of O.
P-methyl benzenesulfonic acid, sodium hydroxide are chemically pure reagent.
Reference Example 1
Resorcinol is added into the 500ml round-bottomed flasks equipped with stirring, temperature control, reflux condenser and dropping funel
1mol, resorcinol are warming up to 130 DEG C of thawings.10min is stirred after catalyst PTSA is added, 0.61mol first is then added dropwise dropwise
Aldehyde.160 DEG C of air-distillation 60min are warming up to, gained 111g resorcinol-formaldehyde resins after 30min are evaporated under reduced pressure.Prepared benzene
109 DEG C of the softening point of fluosite.Free resorcinol is 3.1%.
Reference Example 2
Resorcinol is added into the 500ml round-bottomed flasks equipped with stirring, temperature control, reflux condenser and dropping funel
1mol, resorcinol are warming up to 130 DEG C of thawings.10min is stirred after catalyst PTSA is added, styrene is then added dropwise dropwise
0.4mol keeps 30min after dripping styrene, and 0.63mol formaldehyde is then added dropwise.160 DEG C of air-distillation 60min are warming up to,
Gained 152g styryls resorcinol-resorcinol-formaldehyde resin after vacuum distillation 30min.Prepared phenol formaldehyde resin
107 DEG C of softening point.Free resorcinol is 1.5%.
Reference Example 3
The addition phenol 1mol into the 500ml round-bottomed flasks equipped with stirring, temperature control, reflux condenser and dropping funel, ten
Dialkyl phenol 0.3mol, toluene 30g stir 10min after catalyst PTSA is added, then drip dropwise after being warming up to 100 DEG C of thawings
Add 0.67mol formaldehyde.160 DEG C of air-distillation 60min are warming up to, gained 119g dodecylphenols-benzene after 30min is evaporated under reduced pressure
Resinox.102 DEG C of the softening point of prepared phenol formaldehyde resin.Free-phenol is 1.1%, and dissociate dodecylphenol
4.5%.
Embodiment 1
0.05mol is added into the 500ml round-bottomed flasks equipped with stirring, temperature control, reflux condenser and dropping funel to uncle
At 90 DEG C, first segment aldehyde 0.1mol is added in butylphenol and 0.5g sodium hydroxides and 10g toluene, at 90 DEG C after reaction 1h, adds
Enter 1mol melting phenol, stirs evenly, 2.5g p-methyl benzenesulfonic acids and 1g oxalic acid is added, is warming up to 100 DEG C, is dripped under reflux state
Add second segment aldehyde 0.53mol, after dripping reflux keep 60min, be warming up to 160 DEG C of air-distillations, finally -0.08Mpa~-
Through vacuum distillation dehydration under 0.1Mpa vacuum, it is 112 DEG C to measure resin softening point.Obtain alkyl phenol-phenol-shown in formula (a)
Formaldehyde resin, wherein R are p-tert-butylphenol.
Embodiment 2
0.1mol is added into the 500ml round-bottomed flasks equipped with stirring, temperature control, reflux condenser and dropping funel to special pungent
At 70 DEG C, first segment formaldehyde is added in base phenol and 0.3g sodium hydroxides and 10g toluene, including aldehyde 0.1mol and 0.1mol solid
Aldehyde at 70 DEG C after reaction 3h, is added 1mol and melts phenol, stir evenly, 1.8g p-methyl benzenesulfonic acids are added, are warming up to 100 DEG C,
Second segment aldehyde 0.54mol is added dropwise under reflux state, reflux holding 60min, is warming up to 160 DEG C of air-distillations, finally after dripping
Through vacuum distillation dehydration under -0.08Mpa~-0.1Mpa vacuum, it is 109 DEG C to measure resin softening point.It obtains shown in formula (a)
Alkyl phenol-phenol-formaldehyde resin, wherein R are to tert-octylphenol.
Embodiment 3~5
Dodecylphenol is added into the 500ml round-bottomed flasks equipped with stirring, temperature control, reflux condenser and dropping funel,
With 0.5g sodium hydroxides and 10g toluene, at 70 DEG C, it is added first segment formaldehyde, at 80 DEG C after reaction 2h, 1mol is added and melts benzene
Phenol stirs evenly, and 2.8g p-methyl benzenesulfonic acids are added, are warming up to 100 DEG C, second segment aldehyde is added dropwise under reflux state, after dripping
Reflux keeps 60min, is warming up to 160 DEG C of air-distillations, finally de- through being evaporated under reduced pressure under -0.08Mpa~-0.1Mpa vacuum
Water, obtains alkyl phenol-phenol-formaldehyde resin shown in formula (a), and wherein R is to dodecylphenol.
1. embodiment of table, 3~5 resins synthesis formula
| Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| To dodecylphenol, mol | 0.1 | 0.2 | 0.3 |
| First segment aldehyde, mol | 0.2 | 0.41 | 0.6 |
| Second segment aldehyde, mol | 0.50 | 0.46 | 0.39 |
| Resin softening point, DEG C | 104 | 110 | 103 |
2. Reference Example 1-3 of table, Examples 1 to 5 resin free phenol data
3 rubber applications test formulations of table
Application of 6 resin of embodiment in rubber product
Rubber components are mixed at about 150 DEG C with Banbury mixers, are kneaded and masterbatch is made by the first step
(master batch)。
Second step, respectively by the binder resin sample and cobalt salt prepared by Reference Example 1-3 and Examples 1 to 5, in temperature
At about 145 DEG C, Banbury mixers are mixed into, mixing obtains masterbatch.
Third walks, and mixing is added in insoluble sulfur listed in table 3, accelerating agent, HMMM at 90~100 DEG C, is kneaded
The product of gained is stood overnight in the environment of about 23 DEG C of steady temperature and relative humidity 50%.Then, it is measured at 160 DEG C
Sulphur becomes instrument vulcanization, shape, optimum cure degree, the test data of modification vulcanized rubber composition as shown in table 3.Wherein, it stretches
Performance is tested using GB/T 528-2009, and rubber vulcanization condition is 160 DEG C, 15min before aging, sizing material hot air aging
Condition is 100 DEG C, for 24 hours；Hardness is tested using GB/T 531.1-2008；Curability is to use Alpha
Technologies MDR sulphur becomes instrument, adopts by reference standard：GB/T 16584-1996 and GB/T 1233-2008 standards, 160
DEG C, measure under the conditions of 1 ° of radian and 1.67 hertz.Become in instrument in oscillation disk sulphur, sizing material sample is cut by the oscillation of uniform amplitude
Shear force measures the torque of the oscillation Dropbox under curing temperature in embedded glue sample；Vulcanize item used by all-steel cord bond properties
Part：155 DEG C × 40min, steel cord specification：3+9+15*0.22+1 is tested with standard ASTM D1871-2004.
4 rubber size performance of table
The binder resin that the method for the present invention synthesizes it can be seen from 2 data of table has lower free phenol content, embodiment 1
The free alkyl phenol and free-phenol of resin synthesized by~5 are both less than 1%.It is all alkyl phenol-phenol-formaldehyde resin, Reference Example 3
Using the base catalysis used in the present invention, acid catalysis two-step method, and it is copolymerized to obtain alkyl according to common acid catalysis one-step method
Phenol-phenol-formaldehyde resin, resin free phenol content are compared with resin higher, free alkyl phenol content obtained by the method for the present invention
4.5%, free phenol content 1.1%.
According to 4 data of table it is found that Reference Example 1,2 is resorcinol formaldehyde resin and phenylethene modified resorcinol-
Benzenediol-formaldehyde resin, the respectively variety classes of embodiment 1-5, alkyl phenol-phenol-formaldehyde resin of content, the two phase
Than vulcanization and incipient scorch situation are substantially suitable；Mechanical property is also substantially suitable before and after aging；All-steel cord bond properties is also suitable；
And the all-steel cord bond properties after steam ageing and brine aging, the extraction force after Reference Example 1,2 steam ageings are all reduced to
1200N is hereinafter, the extraction force after brine aging is all reduced to 1600N hereinafter, and resin synthesized by embodiment 1-5, steam ageing
Extraction force afterwards is both greater than 1200N, and the extraction force after brine aging is both greater than 1600N, it can be seen that, the steam of embodiment 1-5
All-steel cord bond properties after aging and brine aging is obviously more preferable.By the preparation side of the present invention it can be seen from 4 data of table
Alkyl phenol-phenol-formaldehyde binder resin prepared by method can substitute presently used completely in terms of rubber with all-steel cord bonding
Resorcinol-formaldehyde resin and alkanisation be modified resorcinol-formaldehyde resin；And resistance to steam ageing and resistance to can be significantly improved
Brine ageing properties, have good market prospects.
3 product of Reference Example is that one-step method is copolymerized alkyl phenol-phenol-formaldehyde resin.Compared with embodiment 1-5, vulcanization and coke
It is substantially suitable to burn situation；Mechanical property is slightly worse before and after aging, all-steel cord bond properties, and extraction force is less than 1600N before aging, then
It is significantly worse than embodiment.The above result shows that alkyl phenol-the phenol-formaldehyde resin synthesized using the method for the present invention, can obtain
Preferable bond properties and resistance to steam ageing and salt water resistance ageing properties.
In embodiment 5,2.8g p-methyl benzenesulfonic acids are being added, after being warming up to 100 DEG C, sampling measures free first therein
Aldehyde 0.34%, it is 0.54% that HPLC, which measures wherein free dodecyl phenol, and free phenol and waste water free formaldehyde data are said
Bright alkyl phenol hydroxymethylation is more abundant, and vacuum distillation dehydration after sampling obtains the product of reaction equation II.Fig. 1 decompressions are steamed
The gpc chromatogram of products therefrom after being dehydrated is evaporated, abscissa is the delivery time, when having reacted stop of the sample in gel chromatographic columns
Between, i.e. molecular size range；Ordinate is electrical signal intensity, has reacted sample concentration.Occur three peaks in figure, one is phenol
Peak (delivery time 36.432min), other two peak, the delivery time is respectively 29.136min and 30.438min, according to point
Son amount calculates, and there are four chain link and three chain links, respectively second step product alkyl phenol-phenol-first respectively for this two parts molecule
Two kinds of structures of urea formaldehyde, i.e.,
With
Demonstrate alkali, structure resin as shown in formula (a) can be prepared in sour two-step catalysis：
Wherein：N=1 or 2.
In one-step method, since phenol activity is high, phenol is preferentially reacted with formaldehyde, and the lower alkyl phenol reaction of activity is slow, meeting
Obtain similar block structure copolymer.Relative to phenol-alkyl resinox structure of one-step synthesis method in Reference Example 3, originally
Invention two-step method can obtain the more uniform copolymeric structure of formula (a), improve dispersion performance, Yi Jiyu of the resin in rubber
The respond of methylene donor.Compared to phenol-alkyl resinox of conventional one-step synthesis method, in alkyl phenol-phenol
Rate of charge under the same conditions, resin-bonding performance and salt water resistance ageing properties and steam ageing-resistant performance synthesized by embodiment 5
It is greatly improved.
The protection content of the present invention is not limited to above example.Without departing from the spirit and scope of the invention, originally
Field technology personnel it is conceivable that variation and advantage be all included in the present invention, and with appended claims be protect
Protect range.
Claims (8)
1. a kind of preparation method of alkyl phenol-phenol-formaldehyde resin, which is characterized in that the described method comprises the following steps：(1)
Alkyl phenol, organic solvent and basic catalyst are added in reactor, first segment aldehyde is added, is reacted under the conditions of 70 DEG C~90 DEG C
1-3 hours, synthesize hydroxymethyl alkyl phenol；(2) phenol and acidic catalyst are added and then into mixture, be warming up to 100 DEG C into
Row reaction；(3) second segment aldehyde is finally added into mixture, reaction heats up after 1-4 hours and is dehydrated, obtains as shown in formula (a)
Alkyl phenol-phenol-formaldehyde resin；
Wherein, R is the alkyl of C4-C20；
N=1 or 2；
M, o are positive integer.
2. preparation method as described in claim 1, which is characterized in that the alkyl contraposition substitution that the alkyl phenol is C4-C20
Alkyl phenol.
3. preparation method as described in claim 1, which is characterized in that the molar ratio of the alkyl phenol and phenol is 0.05-
0.3:1。
4. preparation method as described in claim 1, which is characterized in that the molar ratio of the alkyl phenol and first segment aldehyde is 1:2-
2.5。
5. preparation method as described in claim 1, which is characterized in that the basic catalyst is ammonium hydroxide, alkylamine, dialkyl group
Times of amine, trialkylamine, hexamethylenetetramine, diethanol amine, triethanolamine, alkali metal, alkaline earth oxide, hydroxide
It anticipates a kind of or arbitrary two or more combination.
6. preparation method as described in claim 1, which is characterized in that the acidic catalyst is sulfuric acid, benzene sulfonic acid and its alkane
Any one or any two or more combinations of base substituent, phenol sulfuric acid.
7. a kind of alkyl phenol-phenol-formaldehyde resin, which is characterized in that be made by claim 1 the method, structure such as formula
(a) shown in：
Wherein, R is the alkyl of C4-C20；
N=1 or 2；
M, o are positive integer.
8. alkyl phenol-phenol-formaldehyde resin as claimed in claim 7, which is characterized in that it can be used as rubber adhesion accelerating agent
Applied to tire body cord, tyre surface or rubber cover.
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| CN107459614B (en) * | 2017-08-28 | 2019-07-26 | 上海超程化工科技有限公司 | A kind of environment-friendly type adhesion promotor and preparation method thereof, application |
| CN109134871B (en) * | 2018-07-20 | 2021-06-29 | 彤程化学（中国）有限公司 | Terpene resin modified resorcinol-formaldehyde adhesive resin and preparation method and application thereof |
| CN109160986B (en) * | 2018-08-22 | 2021-08-17 | 江苏麒祥高新材料有限公司 | Modified m-cresol-phenol-formaldehyde resin, preparation method and rubber composition thereof |
| JP7398901B2 (en) * | 2018-08-28 | 2023-12-15 | 旭化成株式会社 | Modified conjugated diene polymer composition, rubber composition, and method for producing rubber composition |
| CN113004476B (en) * | 2019-12-20 | 2023-05-05 | 彤程化学（中国）有限公司 | Phenolic resin with nano-size structure and preparation and application thereof |
| CN112159499B (en) * | 2020-10-09 | 2022-11-18 | 山东阳谷华泰化工股份有限公司 | Grafted alkylphenol phenolic resin and preparation method thereof |
| CN112300349A (en) * | 2020-10-20 | 2021-02-02 | 江苏麒祥高新材料有限公司 | Preparation and application of high-ortho phenolic adhesive resin |
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| CN101628960A (en) * | 2009-08-18 | 2010-01-20 | 柳忠光 | Adhesion-promotion resin and preparation method thereof, and rubber prepared by same |
| CN103183799A (en) * | 2011-12-30 | 2013-07-03 | 江苏国立化工科技有限公司 | Alkyl phenolic resin rubber tackifier and preparation method |
| CN103910839A (en) * | 2013-01-04 | 2014-07-09 | 常州常京化学有限公司 | Preparation method of alkylphenol-phenolic resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101628960A (en) * | 2009-08-18 | 2010-01-20 | 柳忠光 | Adhesion-promotion resin and preparation method thereof, and rubber prepared by same |
| CN103183799A (en) * | 2011-12-30 | 2013-07-03 | 江苏国立化工科技有限公司 | Alkyl phenolic resin rubber tackifier and preparation method |
| CN103910839A (en) * | 2013-01-04 | 2014-07-09 | 常州常京化学有限公司 | Preparation method of alkylphenol-phenolic resin |
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