CN109160986B - Modified m-cresol-phenol-formaldehyde resin, preparation method and rubber composition thereof - Google Patents
Modified m-cresol-phenol-formaldehyde resin, preparation method and rubber composition thereof Download PDFInfo
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- 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
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- C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
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- 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
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- 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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- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C08L9/06—Copolymers with styrene
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Abstract
The invention provides a modified m-cresol-phenol-formaldehyde resin, a preparation method and a rubber composition thereof, wherein the resin is prepared by reacting raw materials comprising cresol, a modifier X, phenol and at least one aldehyde under an acid catalyst, the softening point of the prepared modified m-cresol-phenol-formaldehyde resin is 90-110 ℃, the free phenol in the resin is 0.3-1% of the resin content, the alkyl free phenol is 0.3-1% of the resin content, and the glass transition temperature of the resin is 55-65 ℃. The preparation method is simple and low in cost, and the prepared modified m-cresol-phenol-formaldehyde resin has greatly reduced content of free phenol and free alkylphenol, has the adhesion performance equivalent to that of resorcinol adhesive resin, improves the water resistance of the phenolic adhesive resin and improves the storage performance of products.
Description
Technical Field
The invention relates to the field of rubber processing aids, in particular to a modified m-cresol-phenol-formaldehyde resin, a preparation method and a rubber composition thereof
Background
In the reinforced rubber product, fiber, nylon, steel wire and the like are used as a supporting framework structure, a m-A-white adhesion reinforcing system is used between the supporting framework structure and rubber, so that the adhesion between the rubber and the framework is improved, and resorcinol-hexamethylenetetramine-white carbon black is commonly used at present. In the vulcanization process, the white carbon black catalyzes methylene to give formaldehyde to hexamethylenetetramine to release, and the formaldehyde reacts with resorcinol to form a network structure, so that the mechanical and adhesive properties of vulcanized rubber can be improved.
Because of its low smoke point and high toxicity, resorcinol used in the rubber mixing process is gradually replaced by resorcinol-formaldehyde prepolymer (Wakui SL-3022, Shengquan RT3100, etc.). The resorcinol-formaldehyde resin overcomes the problem of high fuming toxicity of resorcinol to a certain extent, but the resin still contains free resorcinol (1-5%) with a high proportion, and the resorcinol-formaldehyde resin has high hydroxyl content and strong water absorption, is easy to absorb moisture during storage, is not beneficial to storage, and has obviously reduced bonding effect after moisture absorption.
CN106608956A synthesized a new modified phenol-formaldehyde resin, which meets the reinforcing adhesion requirement of resorcinol-formaldehyde resin in rubber, and has lower free phenol and better weather resistance. However, the synthesis method is relatively complicated by two-stage polymerization, and two-stage addition of formaldehyde, namely, first an alkaline method and then an acid method.
The modified m-cresol-phenol-formaldehyde resin synthesized by the method disclosed by the invention is added with a certain amount of trifunctional phenols, so that the crosslinking capacity is kept, the reinforcing and bonding requirements of the resorcinol-formaldehyde resin in rubber are met, the water resistance is better, and the storage is facilitated. The synthesis method is simpler and more direct, a certain amount of m-cresol is used, alkylation reaction is carried out under acid catalysis, the alkylation reaction is used for homogenizing the reaction activity of active m-cresol and phenol, then polymerization is carried out, and vacuum treatment in post-treatment keeps lower content of free phenol, so that the synthesis method is simplified, and the risk of high free phenol in the copolymerization of m-cresol and phenol is avoided.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides the modified m-cresol-phenol-formaldehyde resin which is simple in preparation method, has the advantages of low fuming toxicity, low cost and difficulty in water absorption compared with the prior art, can improve the water resistance of rubber products, and is favorable for storage.
The preparation method of the invention comprises the steps of firstly using an acid catalyst to carry out alkylation modification to homogenize the activity of various phenols, then carrying out polymerization, and then carrying out polymerization to obtain a relatively uniform phenol copolymerization structure, thereby improving the water absorption resistance of the adhesive resin and improving the storage property of the resin.
In one embodiment, the present invention provides a modified m-cresol-phenol-formaldehyde resin characterized by the structural formula as shown in formula (a):
wherein R is aryl, aralkyl, naphthyl and alpha-pinenyl;
z is 0-2, P is 0-2, and is not 0 at the same time;
m and n are positive integers;
the softening point of the modified m-cresol-phenol-formaldehyde resin is 90-110 ℃, the free phenol content in the resin is 0.3-1% of the mass of the resin, the alkyl free phenol content is 0.3-1% of the mass of the resin, and the glass transition temperature of the resin is 55-65 ℃.
Further, the modified m-cresol-phenol-formaldehyde resin is prepared by reacting raw materials comprising cresol, a modifier X, phenol and at least one aldehyde, wherein the modifier X comprises at least one compound represented by the formula (1):
wherein R is aryl, aralkyl, naphthyl or alpha-pinene, preferably phenyl, methylbenzene or ethylbenzene;
in another embodiment, the present invention also provides a method for preparing a modified m-cresol-phenol-formaldehyde resin, the method comprising the steps of:
(1) cresol and catalyst are added into a reactor, and modifier is added under the condition of 120-150℃ for reaction
Adding phenol for 1-3h, wherein the reaction formula is shown as (I);
the molar ratio of phenol to cresol is phenol: cresol ═ 1:0.8 to 1.6, preferably 1: 0.9-1.2;
the cresol is a mixture of m-cresol and p-cresol, wherein the m-cresol content is 70-99.5%, and the preferable content is 80-99.5%;
the catalyst is an acid catalyst, such as one or more of p-toluenesulfonic acid, sulfuric acid, phosphoric acid or oxalic acid;
the proportion of the acid catalyst is 0.2-1.6 percent of the total amount of the phenol, and preferably 0.4-0.8 percent;
r is aryl, aralkyl, naphthyl, alpha-pinene and other groups, preferably phenyl, methylbenzene or ethylbenzene;
the proportion of the modifier is 40 to 50 percent of the molar ratio of the phenol;
(2) cooling to 90-110 deg.C, adding formaldehyde, reacting for 1-4h, heating to dewater, distilling at normal pressure to 160 deg.C,
vacuum distilling at-0.08 mpa for 60min to obtain target alkylphenol formaldehyde resin with reaction formula shown in (II)
The proportion of the formaldehyde is 60-75% of the molar ratio of the phenol;
wherein R is aryl, aralkyl, naphthyl, alpha-pinene, preferably phenyl, methyl benzene or ethyl benzene;
wherein Z is 0-2, p is 0-2, and is not 0 at the same time;
m and n are positive integers.
In another embodiment, the present invention also provides a modified m-cresol-phenol-formaldehyde resin modified rubber composition comprising:
(i) a rubber component selected from natural rubber or synthetic rubber;
(ii) a methylene donor;
(iii) modified m-cresol-phenol-formaldehyde resins as methylene acceptors;
wherein the softening point of the modified m-cresol-phenol-formaldehyde resin is 90-110 ℃, the free phenol in the resin is 0.3-1% of the resin content, the alkyl free phenol is 0.3-1% of the resin content, and the glass transition temperature of the resin is 55-65 ℃;
the structural formula of the modified m-cresol-phenol-formaldehyde resin is shown as the formula (a):
wherein R is aryl, aralkyl, naphthyl or alpha-pinene, preferably phenyl, methylbenzene or ethylbenzene;
z is 0-2, P is 0-2, and is not 0 at the same time;
m and n are positive integers.
Further, the rubber component is natural or synthetic cis-1, 4-polyisoprene, polybutadiene, polychloroprene, copolymers of isoprene and butadiene, copolymers of acrylonitrile and isoprene, copolymers of styrene and butadiene and isoprene, isobutylene rubber and ethylene-propylene rubber, styrene and butadiene copolymers, and mixtures thereof.
The methylene donor is selected from one or more of hexamethylenetetramine, hexamethoxymethylmelamine, hexaethoxymethylmelamine, trioxymethylene and oxymethylene polymers.
Further, the rubber composition further comprises additives: carbon black, silicon dioxide, zinc oxide, a vulcanizing agent, an anti-aging agent, an antioxidant, a softening agent, cobalt salt and the like.
The invention also provides the application of the modified m-cresol-phenol-formaldehyde resin as an adhesion promoter in rubber products. Further rubber products are steel wire coating rubber, tire carcass cords, treads or covering rubber.
The invention also provides application of the modified m-cresol-phenol-formaldehyde resin as an adhesion promoter of rubber in various composite product rubbers with supporting structures and tire rubbers.
The beneficial effect of the invention is that,
(1) the modified m-cresol-phenol-formaldehyde resin is synthesized, the preparation method is simple and direct, the cost is low, and the content of free phenol and alkyl free phenol in the resin is low;
(2) the trifunctional phenols are added in the preparation process, the crosslinking capability is reserved, the tackifying effect equivalent to that of resorcinol adhesive resin can be obtained, and the water resistance and the storage property of the resin are improved due to the reduction of hydroxyl groups.
Drawings
FIG. 1 shows the results of infrared characterization of the resin obtained in example 2.
FIG. 2 the resin obtained in example 2 was tested for glass transition temperature (test temperature-60-150 ℃, temperature ramp rate 10 ℃/min, N2 atmosphere).
Detailed Description
The present invention will be described in further detail with reference to the following specific examples. The procedures, conditions, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art, except for the contents specifically mentioned below, and the present invention is not particularly limited to the contents. The protection of the present invention is not limited to the following examples. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, and the scope of the appended claims is intended to be protected.
In the experiment of the invention, resorcinol, phenol, cresol, p-toluenesulfonic acid (PTSA), oxalic acid, styrene and formaldehyde are all industrial grade.
Comparative example 1
110g (1mol) of resorcinol is added into a 1L four-neck round-bottom flask provided with a stirring, temperature control, reflux condenser and a constant pressure dropping funnel, 0.4g (0.2 mol) of catalyst PTSA0 is added, the temperature is raised to 130 ℃, 62.4(0.6mol) of styrene is dropwise added at 130 ℃, the temperature is kept for 90min after dropwise addition, the temperature is lowered to 100 ℃, 52.3g of 37% formaldehyde (0.62mol) is dropwise added, the temperature is raised and the atmospheric pressure distillation is carried out to 160 ℃, and the reduced pressure distillation at-0.08 mpa is carried out for 60min, thus obtaining 176g of styrene-based resorcinol formaldehyde resin, wherein the softening point of the prepared resin is 100 ℃, and the free phenol is 3.8%. This is a conventional styrene-modified resorcinol-formalin resin (market-brand Huaqi SL-3020 series, Shengquan RT300 series, etc.)
Example 1
Adding 88g (0.8mol) of m-cresol and 2.9g of p-toluenesulfonic acid into a 1L four-neck round-bottom flask provided with a stirring, temperature control, reflux condenser and a constant pressure dropping funnel, heating to 130 ℃, dropwise adding 74.9(0.72mol) of styrene, carrying out heat preservation for 90min after dropwise adding, then adding 94g (1mol) of phenol, then cooling to 100 ℃, dropwise adding 103.0g of 37% formaldehyde (1.22mol), carrying out heat preservation for 90min after dropwise adding, heating, distilling to 160 ℃ under normal pressure, and carrying out reduced pressure distillation at-0.08 mpa for 60min to obtain 258g of modified m-cresol-phenol-formaldehyde resin with a softening point of 105 ℃.
Example 2
176g (1.6mol) of cresol with the content of 70 percent of m-cresol, 1.1g of p-toluenesulfonic acid and 1.1g of oxalic acid are added into a 1L four-mouth round-bottom flask provided with a stirring, temperature control, a reflux condenser tube and a constant-pressure dropping funnel, heated to 130 ℃, dropwise added with 108.2(1.04mol) of styrene, and subjected to heat preservation for 90min after dropwise addition, then added with 94g (1mol) of phenol, cooled to 100 ℃, then added with 155.3g of 37 percent formaldehyde (1.87mol), subjected to heat preservation for 90min after dropwise addition, subjected to normal-pressure distillation to 160 ℃ after heating and subjected to reduced-pressure distillation at-0.08 mpa for 60min to obtain 370g of modified m-cresol-phenol-formaldehyde resin with the softening point of 95 ℃.
Example 3
132g (1.2mol) of m-cresol and 1.36g of p-toluenesulfonic acid are added into a 1L four-mouth round bottom flask provided with a stirring, temperature control, reflux condenser and a constant pressure dropping funnel, wherein the content of the m-cresol is 99.5 percent, the mixture is heated to 130 ℃, 114.4(1.1mol) of styrene is dropwise added, the temperature is kept for 90min after the dropwise addition, 94g (1mol) of phenol is added, the temperature is reduced to 100 ℃, 127.8g of 37 percent formaldehyde (1.54mol) is dropwise added, the temperature is kept for 90min after the dropwise addition, the temperature is increased to 160 ℃ under normal pressure and the distillation temperature is reduced to 60min, and 342g of modified m-cresol-phenol-formaldehyde resin with the softening point of 98 ℃ is obtained.
Specific relevant performance tests are as follows:
(1) the free phenol content results are shown in table 1.
Table 1 examples 1-3 free phenol content of synthetic resins
| Example 1 | Example 2 | Example 3 | |
| Free phenol | 0.5％ | 0.4％ | 0.3％ |
| Free alkyl phenols | 0.6％ | 0.5％ | 0.4％ |
(2) Storage stability test for synthetic resins
Immediately testing the moisture content of the obtained resin by using a Karl Fischer moisture titrator after preparing the finished resin, then placing the resin in two groups under the conditions of 25 ℃ of temperature and 60-80% of humidity for 30 days under open and closed conditions, testing the moisture content of the resin, soaking the resin in 25 ℃ water for 15 days, and testing the moisture content of a sample. The test results are shown in table 2.
Table 2 moisture content test in examples and comparative examples
(3) Use of synthetic resin in rubber products
The experimental formulation is shown in table 3:
TABLE 3 rubber application test formulation
| Serial number | Name (R) | Parts by mass |
| 1 | Natural Rubber (NR) | 100 |
| 2 | Carbon black (N326) | 50 |
| 3 | Silica (silica833) | 10 |
| 4 | Zinc oxide | 8 |
| 5 | Sulfur 80% (ISOT20) | 5 |
| 6 | Cobalt salt | 1 |
| 7 | N- (1, 2-dibutylmethyl) -N' -phenyl-p-phenylenediamine (anti-aging agent 4020) | 1.5 |
| 8 | Polymeric 1, 2-dihydro-2, 2, 4-Trimethylquinoline (TMQ) | 0.5 |
| 9 | HMMM(65％) | 5 |
| 10 | N-tert-butyl-benzothiazole-sulfenamide (TBBS) | 1 |
| 11 | Binder resin (comparative example 1, examples 1 to 3) | 1.8 |
The rubber composition was prepared as follows:
in the first step, the rubber components are mixed at about 150 ℃ using a Farrel internal mixer to prepare a master batch.
In the second step, the resins prepared in comparative example 1 and examples 1 to 3, respectively, were mixed with a cobalt salt at a temperature of about 145 ℃ into a master batch obtained by mixing in a Farrel internal mixer.
And thirdly, adding other components in the table 3 at 90-100 ℃ for mixing, and placing the product modified vulcanized rubber mixture obtained by mixing in an environment with a constant temperature of about 23-25 ℃ and a relative humidity of 40-80% overnight. Then, the mechanical properties were evaluated by measuring the vulcanization rate, the shape and the optimum vulcanization rate at 150 ℃ and the test data of the modified vulcanized rubber composition are shown in Table 4.
Wherein the tensile property is tested by GB/T528-2009; the hardness is tested by GB/T531.1-2008; the sulfuration performance adopts a high-iron sulfur change instrument, and adopts the following standard: GB/T16584-1996 and GB/T1233-2008, measured at 150 ℃, 1 ° arc and 1.67 Hz. In an oscillating disc sulfur analyzer, a rubber material sample is subjected to an oscillating shearing force with constant amplitude, and the torque of an oscillating disc embedded in the rubber material sample at a vulcanization temperature is measured; vulcanization conditions adopted for steel cord adhesion properties (N): the temperature is 155 ℃ and multiplied by 40min, and the specification of the steel cord is high; 3+9+15 x 0.22+1, tested according to the standard ASTM D1871-2004.
TABLE 4 rubber stock Properties
As can be seen from tables 1-2 and 4, the comparative examples and examples are consistent in initial moisture content, but the examples show lower water absorption either after open or closed placement, while in the immersion placement experiments, the resins of the examples were found to possess lower ultimate water absorption, indicating that the prepared modified m-cresol-phenol-formaldehyde resin can achieve adhesion similar to that of the conventional modified resorcinol-formaldehyde resin while ensuring a low free phenol content, and further, a bonded phenolic resin having better water resistance, lower maximum water content and easier storage, and at maximum water content, better adhesion retention than that of the conventional modified resorcinol-formaldehyde resin.
Therefore, the invention provides a modified m-cresol-phenol-formaldehyde resin which can completely replace the resorcinol-formaldehyde resin and alkylated modified resorcinol-formaldehyde resin used at present in the aspect of rubber and steel cord adhesion, has simple preparation method, low cost and low content of free phenol and alkyl free phenol in the resin, and improves the water resistance and storage performance of the resin.
Claims (21)
1. A modified m-cresol-phenol-formaldehyde resin is characterized in that the structural formula is shown as the formula (a):
wherein R is phenyl, methylbenzene, ethylbenzene, naphthyl, alpha-pinene;
z is 0-2, P is not 0;
m and n are positive integers;
the modified m-cresol-phenol-formaldehyde resin is prepared by reacting raw materials comprising cresol, a modifier X, phenol and at least one aldehyde, wherein the modifier X comprises at least one compound shown as the following formula:
wherein R is phenyl, methylbenzene, ethylbenzene, naphthyl, alpha-pinene;
the cresol is a mixture of m-cresol and p-cresol.
2. The modified m-cresol-phenol-formaldehyde resin as claimed in claim 1, characterized in that: the softening point of the resin is 90-110 ℃.
3. The modified m-cresol-phenol-formaldehyde resin as claimed in claim 1, characterized in that: the content of free phenol in the resin is 0.3-1% of the mass of the resin.
4. The modified m-cresol-phenol-formaldehyde resin as claimed in claim 1, characterized in that: the content of the alkyl free phenol in the resin is 0.3-1% of the mass of the resin.
5. The modified m-cresol-phenol-formaldehyde resin as claimed in claim 1, characterized in that: the glass transition temperature of the resin is between 55 and 65 ℃.
6. The process for producing a modified m-cresol-phenol-formaldehyde resin as claimed in any one of claims 1 to 5, wherein: the method comprises the following steps:
(1) cresol and a catalyst are added into a reactor, a modifier X is added under the condition of 120-150 ℃ for reaction for 1-3h, and then phenol is added, wherein the reaction formula is shown as (I):
(2) cooling to 90-110 ℃, adding formaldehyde, reacting for 1-4h, heating to dewater, distilling to 160 ℃ under normal pressure, and distilling under reduced pressure of-0.08 mpa for 60min to obtain the target alkylphenol-formaldehyde resin, wherein the reaction formula is shown as (II):
wherein R is phenyl, methylbenzene, ethylbenzene, naphthyl, alpha-pinene;
z is 0-2, P is not 0;
m and n are positive integers.
7. The process according to claim 6, wherein the cresol is a mixture of m-cresol and p-cresol, and the m-cresol content is 70-99.5%.
8. The process according to claim 6, wherein the molar ratio of phenol to cresol is phenol: cresol ═ 1: 0.8-1.6.
9. The process according to claim 6, wherein the proportion of the modifier X is 40 to 50% by mole based on the total phenols.
10. The method of claim 6, wherein: the proportion of the formaldehyde is 60-75% of the total mole number of the phenol.
11. A rubber composition comprising
(i) A rubber component selected from natural rubber or synthetic rubber;
(ii) a methylene donor;
(iii) a methylene acceptor;
the method is characterized in that: the methylene acceptor is the modified m-cresol-phenol-formaldehyde resin as set forth in any one of claims 1 to 5 or the modified m-cresol-phenol-formaldehyde resin prepared by the preparation method as set forth in any one of claims 6 to 10.
12. The rubber composition of claim 11, wherein the resin has a softening point of 90 to 110 ℃.
13. The rubber composition of claim 11, wherein the free phenol content of the resin is 0.3 to 1% of the resin content.
14. The rubber composition of claim 11, wherein the free alkylphenol content of the resin is 0.3 to 1% of the resin content.
15. The rubber composition of claim 11, wherein the resin has a glass transition temperature of between 55 ℃ and 65 ℃.
16. The rubber composition of claim 11, wherein the rubber component is cis-1, 4-polyisoprene, polybutadiene, polychloroprene, copolymers of isoprene and butadiene, copolymers of acrylonitrile and isoprene, copolymers of styrene and butadiene and isoprene, isobutylene rubber and ethylene-propylene rubber, styrene and butadiene copolymers, and mixtures thereof.
17. The rubber composition of claim 11, wherein the methylene donor is selected from one or more of hexamethylenetetramine, hexamethoxymethylmelamine, hexaethoxymethylmelamine, and oxymethylene polymers.
18. The rubber composition of claim 11, further comprising additives: carbon black, silicon dioxide, zinc oxide, a vulcanizing agent, an anti-aging agent, an antioxidant, a softening agent and cobalt salt.
19. Use of the modified m-cresol-phenol-formaldehyde resin as claimed in any of claims 1 to 5 or as prepared by the preparation process as claimed in any of claims 6 to 10 as adhesion promoter in rubber articles.
20. The use according to claim 19, said rubber article being a steel wire overlay, a tire carcass cord, a tread or an overlay rubber.
21. A rubber article comprising the modified m-cresol-phenol-formaldehyde resin as claimed in any of claims 1 to 5 or comprising the rubber composition as claimed in any of claims 11 to 18.
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| JP7372529B2 (en) * | 2019-10-03 | 2023-11-01 | 横浜ゴム株式会社 | Rubber composition for adhering steel cords and conveyor belts |
| CN110903445B (en) * | 2019-11-30 | 2022-06-03 | 浙江自立高分子化工材料有限公司 | Phenolic resin for coil framework and preparation method thereof |
| CN114437361B (en) * | 2021-12-24 | 2022-12-06 | 中国科学院福建物质结构研究所 | Inorganic-organic hybrid material, preparation method thereof and application of modified polyurethane prepared from inorganic-organic hybrid material as adhesive |
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