阅读说明：本技术 一种低生热功能树脂及其制备方法和应用 (Low-heat-generation functional resin and preparation method and application thereof ) 是由 彭华龙 李斌斌 付哲 徐黎明 于 2021-08-31 设计创作，主要内容包括：本发明提供了一种低生热功能树脂,其特征在于,结构通式如下：其中,R表示R-(1)为或饱和烷烃链,R-(2)为或不饱和烯烃链,m为1-10的整数,q为1-10的整数；n为0-3整数。本发明提供的低生热功能树脂可以使得填料在橡胶基体中分散更为均匀,减少应力集中点的出现。同时,酚羟基可以减少白炭黑的团聚,改善白炭黑在基体中的分散,综合以上优势,从而达到改善树脂应用性能的效果。(The invention provides a low-heat-generation functional resin which is characterized by comprising the following structural general formula: wherein R represents R 1 Is composed of Or Saturated alkane chain, R 2 Is composed of Or An unsaturated olefin chain, m is an integer of 1 to 10, q is an integer of 1 to 10; n is an integer of 0 to 3. The low-heat-generation functional resin provided by the invention can enable the filler to be dispersed in the rubber matrix more uniformly, and reduce the occurrence of stress concentration points. Meanwhile, the phenolic hydroxyl can reduce the agglomeration of the white carbon black, improve the dispersion of the white carbon black in a matrix, and integrate the advantages, thereby achieving the effect of improving the application performance of the resin.)

1. A low heat generation functional resin is characterized in that the structural general formula is as follows:

wherein R representsR₁Is composed ofSaturated alkane chain, R₂Is composed ofAn unsaturated olefin chain, m is an integer of 1 to 10, q is an integer of 1 to 10; n is an integer of 0 to 3.

2. The low heat generating functional resin according to claim 1, wherein the reaction formula for producing the low heat generating functional resin is as follows:

wherein the content of the first and second substances,has an iodine value of 30-250gI₂100g of at least one resin, the iodine value is detected according to GB/T5532-2008;

p is an integer of 1 to 10, and p-q representsThe number of olefin double bonds not involved in the reaction in the structure.

3. The low heat generating functional resin according to claim 1, wherein the iodine value of the low heat generating functional resin is 20 to 130gI₂/100g。

4. A method for producing a low heat generating functional resin according to claim 1, characterized by comprising the steps of:

dissolving R resin in an organic solvent to form a resin solution, mixing an acidic catalyst and cardanol, then dropwise adding the mixture into the resin solution at a controlled temperature, reacting at a controlled temperature after the dropwise adding is finished, then adding a terminator, purifying, distilling to remove solvent, and granulating to obtain the low-heat-generation functional resin;

wherein the structural formula of the R resin is shown in the specificationR resin is selected from resin with iodine value of 30-250gI₂At least one of the resins per 100g, the iodine value is determined according to GB/T5532-2008.

5. The method for preparing a low heat generating functional resin according to claim 4, wherein the cardanol is used in an amount of 0.5 to 30 wt% of the R resin.

6. The method for producing a low-heat generating functional resin according to claim 4, wherein the catalyst is added in an amount of 0.1 to 5 wt% based on the R resin.

7. The method for preparing a low heat generating functional resin according to claim 4, wherein the organic solvent is at least one selected from the group consisting of toluene, xylene, methylene chloride, cyclohexane, methylcyclohexane, ethyl acetate and dioxane, and is used in an amount of 30 to 200 wt% based on the R resin.

8. The method for preparing a low-heat generating functional resin according to claim 4, wherein the acidic catalyst is at least one selected from the group consisting of aluminum trichloride, ferric trichloride, zinc chloride, boron trifluoride gas, boron trifluoride complex, sulfuric acid, p-toluenesulfonic acid and phosphoric acid.

9. The method for producing a low heat generating functional resin according to claim 4, wherein the terminator is a solution formed of at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate or sodium hydrogencarbonate.

10. Use of the low heat generating functional resin according to any one of claims 1 to 3 or the low heat generating functional resin produced by the method according to any one of claims 4 to 9 in a tire rubber.

Technical Field

The invention belongs to the technical field of modified resin preparation, and particularly relates to a low-heat-generation functional resin, and a preparation method and application thereof.

Background

With the continuous improvement of living standard of people, higher requirements are provided for the demand and quality of automobiles, and simultaneously higher requirements are provided for the tire industry. The European Union tire labeling method is formally implemented in 2012, 11 months and 1 days, and China also implements a tire labeling system in 2016. With the implementation of the labeling method, higher requirements are also put on the quality and performance of the tire, including the safety performance, the energy consumption performance, the wear resistance performance and the like of the tire. Therefore, how to balance the relationship among wet skid resistance, rolling resistance and wear resistance is an important problem in developing high-performance green tires.

Aiming at the problem of 'magic triangles' in tires, the use of resin functional additives provides a feasible scheme for improving the wet skid resistance of rubber. The addition of the oligomer resin shifts the glass transition temperature of the rubber system to high temperatures, thereby improving the wet skid resistance of the tire system. However, as the glass transition temperature of the system moves to a high temperature, the tan delta value at 0 ℃ of the sizing material is increased, and the tan delta value at 60 ℃ is also prevented from being increased, so that the rolling resistance, namely the oil consumption, is increased. Therefore, how to balance the relationship between the two is an important difficulty.

The research process finds that the oligomer resin often contains a large amount of unreacted double bonds, and a proper amount of double bonds can participate in crosslinking in the process of rubber vulcanization, so that the crosslinking density of a system is increased, the compatibility of the resin and rubber is improved, and a certain effect on balancing rolling resistance and wet slip is achieved. However, in the preparation of oligomer resins by polymerization of monomers, there is a need for an adequate means for effective control of the unreacted double bonds therein.

1) When too many unreacted double bonds exist in the resin, the too many unreacted double bonds consume the complex of the sulfur and the accelerator, so that the active complex for crosslinking the rubber is reduced, the vulcanization time is prolonged, the vulcanization strength is reduced, and the defects of increase of the vulcanization time and increase of energy consumption are caused in the process; the performance of the vulcanized rubber causes the wet skid, wear resistance and hardness deterioration of the vulcanized rubber, so that the service life of the tire is reduced, and meanwhile, after the double bonds consume a complex for rubber crosslinking, the content of the double bonds in the rubber is increased, so that the ozone, thermal oxidation and photo-oxidation aging resistance of the rubber is deteriorated, and finally, the tire is easy to crack in the use process, and the service life and safety performance of the tire are reduced.

2) When the double bond content in the resin is low, the resin can only pass through intermolecular forces with the rubber, such as: van der Waals force, hydrogen bonds and the like are dispersed in a rubber matrix, the bonding force between resin and rubber is weak, the resin is easily dispersed unevenly, so that the filler is dispersed poorly, the processability of the rubber is deviated, the glass transition temperature of the rubber material cannot be effectively increased, and the wet skid resistance of the rubber is improved.

Therefore, how to effectively control the double bond content, i.e. the degree of unsaturation, in the oligomer resin is also one of the key points for improving the balance application performance of the resin functional auxiliary in the rubber system.

Resin hydrogenation is a common method at present for how to control the degree of unsaturation of the resin. Although resin hydrogenation can reduce the degree of unsaturation of the resin, the method also has more limitations: 1) the hydrogenation reaction has no selectivity and can change all unsaturated double bonds in the resin into unsaturated double bondsSaturated single bond, lowering iodine value of resin to near 0g I₂100g, which causes the partial aromatic hydrocarbon structure to be changed into a naphthenic hydrocarbon structure, so that the rigid structure of the resin is reduced, the glass transition temperature is reduced, the Tan delta peak value of the vulcanized rubber is shifted to the left, and the wet skid resistance is weakened; 2) the aromatic hydrocarbon structure is changed into a naphthenic hydrocarbon structure, so that the compatibility of the resin and other additives is slightly poor, the filler is easily dispersed unevenly, and the stress concentration phenomenon is easy to occur; 3) the resin unsaturation degree is reduced through a hydrogenation process, the process is complex, high temperature of 300 ℃ and high pressure of 15-25MPa are usually required, the requirement on equipment is high, the energy consumption is high, the danger of the process is high due to the use of hydrogen, meanwhile, the catalyst used for hydrogenation is a noble metal catalyst, the catalyst is extremely easy to inactivate in the reaction process, the recovery rate of the catalyst is low, and the cost of the catalyst is high. The resin is used as a plasticizer auxiliary agent in rubber, and has low market price and small dosage. Therefore, the method for reducing the resin unsaturation degree by adopting the hydrogenation process with complex process, high cost and great danger has lower economic benefit in the tire industry.

Therefore, it is necessary to develop a method capable of effectively controlling the unsaturation degree of the resin, so as to overcome the defects of the functional resin in rubber applications.

Disclosure of Invention

The invention provides a low-heat-generation functional resin and a preparation method thereof, which can effectively regulate and control the unsaturation degree of the functional resin, improve the defects of the functional resin in rubber application and overcome the defects of the prior art.

The method is realized by the following technical scheme:

a low heat generation functional resin has the following structural general formula:

wherein R representsR₁Is composed ofSaturated alkane chain, R₂Is composed ofAn unsaturated olefin chain, m is an integer of 1 to 10, q is an integer of 1 to 10; n is an integer of 0 to 3.

Further, the reaction formula for producing the low heat generating functional resin is as follows:

wherein the content of the first and second substances,has an iodine value of 30-250gI₂100g of at least one resin, the iodine value is detected according to GB/T5532-2008;

p is an integer of 1 to 10, and p-q representsThe number of olefin double bonds not involved in the reaction in the structure.

Further, the iodine value of the low heat generating functional resin is 20-130gI₂/100g。

The invention also provides a preparation method of the low-heat-generation functional resin, which comprises the following steps:

dissolving R resin in an organic solvent to form a resin solution, mixing an acidic catalyst and cardanol, then dropwise adding the mixture into the resin solution at a controlled temperature, reacting at a controlled temperature after the dropwise adding is finished, then adding a terminator, purifying, distilling to remove solvent, and granulating to obtain cardanol modified resin;

wherein the structural formula of the R resin is shown in the specificationWherein m is an integer of 1-10, and p is an integer of 1-10; r resin is selected from resin with iodine value of 30-250gI₂At least one of the resins per 100g, the iodine value being determined according to GB/T5532-。

The cardanol is used for modifying the resin, the unsaturation degree of the resin can be selectively regulated and controlled by adjusting the reaction ratio of the cardanol, meanwhile, due to the introduction of the cardanol in the resin, long-linear alkane of a side chain of the cardanol has excellent compatibility with a rubber matrix, and the benzene ring structure of the cardanol is similar to that of other auxiliary agents in the rubber, so that the filler can be dispersed in the rubber matrix more uniformly, and the occurrence of stress concentration points is reduced. Meanwhile, the phenolic hydroxyl is expected to reduce the agglomeration of the white carbon black, improve the dispersion of the white carbon black in a matrix, and integrate the advantages, thereby achieving the effect of improving the application performance of the resin.

Further, the dosage of the cardanol is 0.5-30 wt% of that of the R resin.

Further, the amount of the catalyst added is 0.1 to 5 wt% of the R resin, and if the amount of the catalyst is too small, the catalytic activity is insufficient, and if the amount of the catalyst is too large, the cost is increased.

Further, the organic solvent is at least one selected from toluene, xylene, dichloromethane, cyclohexane, methylcyclohexane, ethyl acetate or dioxane, and the amount of the organic solvent is 30 to 200 wt% of the R resin.

Further, the acidic catalyst is selected from at least one of aluminum trichloride, ferric trichloride, zinc chloride, boron trifluoride gas, boron trifluoride complex, sulfuric acid, p-toluenesulfonic acid, or phosphoric acid.

The acidic catalyst and the cardanol are firstly mixed and then are dropwise added into a reaction system together, so that firstly, violent heat release caused by the one-time addition of the catalyst can be avoided, the reaction is more stable, secondly, the acidic catalyst and the cardanol are firstly mixed and then are dropwise added together, the activity of the catalyst can be ensured, the reaction efficiency is improved, and if the acidic catalyst and the cardanol are firstly added, the activity of the catalyst can be weakened or inactivated along with the prolonging of time as the catalyst is firstly added; thirdly, the acidic catalyst and the cardanol are mixed and then are dripped, the reaction of the cardanol and the double bonds can be controlled in a targeted manner, the purpose of regulating and controlling the iodine value is achieved, and the side reaction between the double bonds of the resin caused by the existence of excessive catalyst is avoided.

The concentration and the active center of the catalyst in the reaction system can be effectively controlled, the reaction process is relatively milder and more stable, the selective modification is facilitated, the dropwise addition reaction has no obvious heat release phenomenon, and the process is safer.

Further, the temperature of the temperature-controlled dropwise addition is 30-140 ℃.

Further, the temperature of the temperature-controlled reaction is 30-140 ℃.

Further, the terminator is a solution formed by at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate or sodium bicarbonate, wherein the sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate or sodium bicarbonate is used as a solute, and the solute is used in an amount of 0.1-10 wt% of the R resin.

The invention also provides application of the low heat generation functional resin in tire rubber, in particular application of improving wet skid resistance and reducing rolling resistance in the tire rubber.

Compared with the prior art, the invention has the following advantages:

1. the resin is chemically modified by cardanol, the iodine value of the resin is selectively regulated and controlled, the problem that the unsaturation degree is uncontrollable during polymerization preparation of the resin is solved, and meanwhile, the iodine value of the resin is regulated to a proper position through modification, so that the resin can exert better application performance in tire rubber;

2. the cardanol is purified in natural cashew nut shell oil, the preparation method is environment-friendly, the preparation process is simple, the reaction conditions are mild and safe, the modification cost is low, the economic benefit is high, the iodine value (namely the degree of unsaturation) of the resin can be selectively regulated, and the performance of the resin after the cardanol is modified is obviously improved. The problems of high cost, high safety risk and uncontrollable selectivity of the resin hydrogenation process are solved.

Drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.

FIG. 1 is an infrared spectrum of a low heat generating functional resin prepared in example 1 of the present invention;

FIG. 2 is an infrared spectrum of the phenolic hydroxyl group of FIG. 1;

FIG. 3 is an infrared spectrum of the double bond of FIG. 1;

FIG. 4 is a hydrogen nuclear magnetic resonance spectrum of a low heat generating functional resin prepared in example 1 of the present invention;

FIG. 5 is an infrared spectrum of a low heat generating functional resin prepared in example 2 of the present invention;

FIG. 6 is an infrared spectrum of the phenolic hydroxyl group of FIG. 5;

FIG. 7 is an infrared spectrum of the double bond of FIG. 5.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The technical problem of how to balance the wet skid resistance and the rolling resistance is usually solved by silane modification in the field, and groups which can react with rubber fillers, such as methoxyl group or ethoxyl group, can be introduced into resin after silane modification, so that the dispersion of the fillers is promoted, the agglomeration is avoided, and the purpose of reducing the rolling resistance is achieved.

In the research process, the inventor finds that a large number of unreacted double bonds are often contained in oligomer resin, so the invention provides a method for regulating and controlling the unsaturation degree of functional resin, which has the following principle: by adjusting the content of double bonds, a proper amount of double bonds can participate in crosslinking in the process of vulcanizing the rubber material, so that the crosslinking density of a system is increased, the compatibility of resin and rubber is improved, and a certain effect on balancing rolling resistance and wet slip is achieved; the invention is different from the principle of adopting silane modification in the prior art, the action principle of adopting silane modification is to improve the dispersion of the filler and prevent the filler from agglomerating to achieve the purpose of reducing the rolling resistance, but the invention adjusts the double bond content in the resin, and a proper amount of double bonds on the resin can participate in the vulcanization process of rubber to improve the crosslinking density so as to achieve the purpose of reducing the rolling resistance, thereby reducing the heat generation of the rubber, so the obtained modified resin is defined as the resin with low heat generation function.

The structural general formula of the low heat generation functional resin is as follows:

wherein R representsR₁Is composed ofSaturated alkane chain, R₂Is composed ofAn unsaturated olefin chain, m is an integer of 1 to 10, q is an integer of 1 to 10; n is an integer of 0 to 3.

The reaction formula for forming the low heat generating functional resin is as follows:

wherein the content of the first and second substances,has an iodine value of 30-250gI₂100g of at least one resin, the iodine value is detected according to GB/T5532-2008;

p is an integer of 1 to 10, and p-q representsThe number of olefin double bonds not involved in the reaction in the structure.

Preparation of the resulting low-heat generating functional resinIodine value of 20-130gI₂/100g。

< detection method and detection apparatus >

Detecting the iodine value according to GB/T5532-2008;

the wax cloud point detection method comprises the following steps: mixing paraffin/EVA/resin at a mass ratio of 25:30:45, heating and stirring uniformly to a clear state, and naturally cooling, wherein the temperature when white mist appears on the wall of the test tube is a wax mist point;

infrared employs fourier infrared spectroscopy (FTIR), in GB; 21186-2007;

the nuclear magnetic hydrogen spectrum is detected by BRUKER AVANCE 400M.

Example 1 (resin A: Cardanol-C9 resin preparation)

The preparation process comprises the following steps:

firstly, the iodine value is 131gI₂100g of hot polymerization C9 resin is dissolved in 80 wt% of toluene solvent to form resin liquid (in the preparation process of the embodiment, the material proportion is based on the mass of the hot polymerization C9 resin, for example, 80 wt% of toluene solvent represents that the amount of the toluene solution is 80% of the mass of the hot polymerization C9 resin, and the manner of representing the amounts of the other components is the same, in other embodiments, the amounts of the components except the resin are based on the mass of the resin used in the embodiment), then 1.2 wt% of aluminum trichloride catalyst and 15 wt% of cardanol are uniformly mixed, then the mixed liquid of the catalyst and the cardanol is uniformly dripped into the resin liquid, and the dripping temperature is controlled to be 75-85 ℃; after the dropwise addition, controlling the reaction temperature to be 120 ℃ and reacting for 6 hours; and after the reaction is finished, adding 3 wt% of sodium hydroxide solution to terminate the reaction, washing the polymerization solution, purifying, distilling, desolventizing and granulating to obtain the cardanol modified C9 resin A, wherein the cardanol modified C9 resin A is the low-heat-generation functional resin.

And (3) index detection and structural analysis of the resin A:

test items	C9 resin	Resin A
			Iodine value/gI2/100g	131	87
Wax cloud point/° c	110	102

Through iodine value comparison, the iodine value of the modified resin A is reduced by about 44, which shows that the unsaturation degree of the C9 resin is reduced through modification; the wax haze point of the modified C9 resin is also reduced, which shows that the compatibility of the modified C9 resin and a rubber matrix is better;

the resin A is subjected to structural analysis, and an infrared spectrogram is shown in figure 1, and a nuclear magnetic hydrogen spectrogram is shown in figure 2. The infrared spectrogram shows that: the C9 resin is modified by cardanol and then reaches the temperature of 1500-1700cm^-1The double bond stretching vibration peak is reduced, thereby further proving that the unsaturation degree of the C9 resin can be controlled by cardanol modification, and meanwhile, the modified resin A is 3200-one 3700cm^-1The peak of phenolic hydroxyl group is obviously increased relative to the C9 resin, thus proving that cardanol successfully modifies the C9 resin; by comparing nuclear magnetic hydrogen spectrograms of the C9 resin and the resin A, obvious phenolic hydroxyl hydrogen appears in the nuclear magnetic hydrogen spectrogram of the C9 resin after modification, and simultaneously, due to the introduction of cardanol side chain long aliphatic hydrocarbon, the aliphatic hydrogen peak of the resin A at the position of 0.9-2.5ppm displacement is obviously enhanced, so that the nuclear magnetic hydrogen spectrogram comparison can further prove that the modified resin structure is formed; combining the above test data, cardanol has been grafted on the resin by modification, and a modified resin of the following structure was obtained:

example 2 (resin B: preparation of Cardanol-C9 resin in different proportions)

Adjusting the proportion of cardanol to obtain modified resins with different iodine values

The catalyst aluminum trichloride in the preparation process of the example 1 is replaced by 1.8 wt%, the cardanol is replaced by 25 wt%, and the rest is unchanged. Finally, cardanol modified C9 resin B is obtained, and the cardanol modified C9 resin B is the low-heat-generation functional resin.

And (3) resin B index detection and structural analysis:

test items	C9 resin	Resin B
			Iodine value/gI2/100g	131	56
Wax cloud point/° c	110	97

Through iodine value comparison, the iodine value of the modified resin B is reduced by about 75, which shows that the unsaturation degree of the C9 resin is obviously reduced after modification; the wax haze point of the modified C9 resin is also obviously reduced, which indicates that the modified C9 resin has better compatibility with a rubber matrix;

and (3) carrying out infrared detection on the resin B, wherein an infrared spectrogram is shown in figure 3, and the infrared spectrogram can show that: the C9 resin is modified by cardanol and then reaches the temperature of 1500-1700cm^-1The double bond stretching vibration peak is obviously reduced, thereby further proving that the double bond content of the C9 resin can be controlled by adjusting the proportion content of cardanol, and the modified resin B is 3200-one 3700cm^-1The peak of phenolic hydroxyl groups is increased more obviously relative to that of the C9 resin, because the increase of the content of cardanol causes more resin to react with cardanol, so that more phenolic hydroxyl groups are introduced, and the cardanol is proved to successfully modify the C9 resin; combining the above test data, cardanol has been grafted on the resin by modification, and a modified resin of the following structure was obtained:

example 3 (resin C: preparation of Cardanol-C5 resin)

The preparation process comprises the following steps:

firstly, the iodine value is 157gI₂Dissolving 100g of C5 resin in a 50 wt% xylene solvent to form a resin solution (the material proportion in the preparation process is based on the mass of the C5 resin), uniformly mixing 1 wt% of aluminum trichloride catalyst and 15 wt% of cardanol, dropwise adding the mixed solution of the catalyst and the cardanol into the resin solution at a constant speed, and controlling the dropwise adding temperature to be 75-85 ℃; after the dropwise addition, controlling the reaction temperature to be 120 ℃ and reacting for 6 hours; and after the reaction is finished, adding 3 wt% of sodium hydroxide solution to terminate the reaction, washing the polymerization solution, purifying, distilling, desolventizing and granulating to obtain the cardanol modified C5 resin C, wherein the cardanol modified C5 resin C is the low-heat-generation functional resin.

And (3) resin C index detection and structural analysis:

test items	C5 resin	Resin C
			Iodine value/gI2/100g	157	90
Wax cloud point/° c	93	86

Through iodine value comparison, the iodine value of the modified resin C is reduced by about 67, which shows that the unsaturation degree of the modified resin C5 is obviously reduced; the iodine value of the modified C5 resin is obviously reduced compared with that of the modified C9 resin under the same cardanol dosage because the C5 resin has more double bond content and more active sites; the wax haze point of the modified C5 resin is obviously reduced, which shows that the modified C5 resin has better compatibility with a rubber matrix.

Example 4 (resin D: preparation of Cardanol-C5/C9 Co-Polymer resin)

The preparation process comprises the following steps:

firstly, the iodine value is 138gI₂100g of C5/C9 copolymer resin is dissolved in 80 wt% of toluene solvent to form resin liquid (the material proportion in the preparation process is based on the mass of the C5/C9 copolymer resin), then 0.6 wt% of boron trifluoride diethyl etherate catalyst and 15 wt% of cardanol are uniformly mixed, the mixed liquid of the catalyst and the cardanol is dripped into the resin liquid at a constant speed, and the dripping temperature is controlled to be 80-90 ℃; after the dropwise addition, controlling the reaction temperature to be 110 ℃ and reacting for 6 h; and after the reaction is finished, adding 1 wt% of sodium hydroxide solution to terminate the reaction, washing the polymerization solution, purifying, distilling, desolventizing and granulating to obtain the cardanol modified C5/C9 copolymer resin D, wherein the cardanol modified C5/C9 copolymer resin D is the low-heat-generation functional resin.

And (3) detecting indexes of the resin D and analyzing the structure:

test items	C5/C9 copolymer resin	Resin D
			Iodine value/gI2/100g	138	75
Wax cloud point/° c	97	91

Through iodine value comparison, the iodine value of the modified resin D is reduced by about 63, which shows that the unsaturation degree of the C5/C9 copolymer resin is obviously reduced after modification; the wax haze point of the modified C5/C9 copolymer resin is obviously reduced, which shows that the modified C5/C9 copolymer resin has better compatibility with a rubber matrix.

Example 5 (resin E: Cardanol-terpene resin preparation)

The preparation process comprises the following steps:

firstly, the iodine value is 143gI₂Dissolving 100g of terpene resin in 80 wt% of toluene solvent to form resin liquid (the mass of the terpene resin is taken as the reference in the preparation process of the resin liquid), then uniformly mixing 1.2 wt% of aluminum trichloride catalyst and 20 wt% of cardanol, dropwise adding the mixed liquid of the catalyst and the cardanol into the resin liquid at constant speed, and controlling the dropwise adding temperature to be 65-75 ℃; after the dropwise addition, controlling the reaction temperature to be 90 ℃ and reacting for 6 hours; and (3) after the reaction is finished, adding a 3 wt% sodium hydroxide solution to terminate the reaction, washing and purifying the polymerization solution, distilling and desolventizing, and granulating to obtain the cardanol modified terpene resin E.

And (3) resin E index detection and structural analysis:

test items	Terpene resin	Resin E
			Iodine value/gI2/100g	143	96
Wax cloud point/° c	104	99

Through iodine value comparison, the iodine value of the modified resin E is reduced by nearly 47, which shows that the unsaturation degree of the terpene resin is obviously reduced after modification; the wax haze point of the modified terpene resin is obviously reduced, which shows that the terpene resin has better compatibility with the rubber matrix after being modified.

Example 6 (resin F: Cardanol-DCPD resin preparation)

The preparation process comprises the following steps:

firstly, the iodine value is 205gI₂Dissolving 100g of DCPD resin in 80 wt% of toluene solvent to form resin liquid (the material proportion in the preparation process is based on the mass of the DCPD resin), then uniformly mixing 1.8 wt% of aluminum trichloride catalyst and 20 wt% of cardanol, dropwise adding the mixed liquid of the catalyst and the cardanol into the resin liquid at constant speed, and controlling the dropwise adding temperature to be 85-95 ℃; after the dropwise addition, controlling the reaction temperature to be 120 ℃ and reacting for 6 hours; and after the reaction is finished, adding 3.2 wt% of sodium hydroxide solution to terminate the reaction, washing and purifying the polymerization solution, distilling and desolventizing, and granulating to obtain the cardanol modified DCPD resin F, wherein the cardanol modified DCPD resin F is the low-heat-generation functional resin disclosed by the application.

And (3) resin F index detection and structural analysis:

test items	DCPD resin	Resin F
			Iodine value/gI2/100g	205	152
Wax cloud point/° c	94	84

Through iodine value comparison, the iodine value of the modified resin F is reduced by about 53, which shows that the unsaturation degree of the DCPD resin is obviously reduced after modification; the wax haze point of the DCPD resin is obviously reduced after the DCPD resin is modified, which shows that the DCPD resin has better compatibility with a rubber matrix after the DCPD resin is modified.

Example 7 (resin G: preparation of Cardanol-coumarone resin)

The preparation process comprises the following steps:

firstly, the iodine value is 129gI₂Dissolving 100g of coumarone resin in 80 wt% of toluene solvent to form a resin solution (the material proportion in the preparation process is based on the mass of the coumarone resin), uniformly mixing 1.2 wt% of aluminum trichloride catalyst and 15 wt% of cardanol, dropwise adding the mixed solution of the catalyst and the cardanol into the resin solution at a constant speed, and controlling the dropwise adding temperature to be 75-85 ℃; after the dropwise addition, controlling the reaction temperature to be 120 ℃ and reacting for 6 hours; after the reaction is finished, adding 3 wt% of sodium hydroxide solution to terminate the reaction, and washing and purifying the polymerization solutionAnd then distilling and desolventizing, and granulating to obtain the cardanol modified coumarone resin G, wherein the cardanol modified coumarone resin G is the low-heat-generation functional resin.

Resin G index detection and structural analysis:

test items	Coumarone resin	Resin G
			Iodine value/gI2/100g	129	89
Wax cloud point/° c	107	101

Through iodine value comparison, the iodine value of the modified resin G is reduced by about 40, which shows that the unsaturation degree of the coumarone resin is obviously reduced after modification; the wax haze point of the modified coumarone resin is obviously reduced, which shows that the modified coumarone resin has better compatibility with a rubber matrix.

And (3) application performance testing:

< Source and specification of raw Material >

Styrene butadiene rubber NS460, Dongguan Tuokkai trade Co., Ltd

Butadiene rubber BR, Peking Yanshan petrochemical rubber and Plastic chemical responsibility Co Ltd

White carbon Silica833, Hencui silicon Ltd

Silane coupling agent Si-69, Degussa Germany

Zinc oxide (ZnO-80), Snless Noman polymers, Inc.;

stearic acid, Nantong Yu Hao chemical technology Co., Ltd

Anti-aging agent 4020, Kailun chemical Limited liability company of Henan

Paraffin 9332F, Hansheng chemical (Fushun) Co., Ltd

Antioxidant RD, Henan Kaolun chemical Limited liability company

Sulfur (S-80), Snless Nomann Polymer materials Ltd

Accelerator NS-80, Snless Nomann Polymer materials Ltd

Accelerant DPG, Kaolun chemical engineering, Inc. of Henan province

< instrumentation >

Model 87-M-3104 open mill, product of Raylel of America Farad

BR1600 internal mixer, product of Farrel America

In order to test the application properties of different modified petroleum resins prepared by the invention, resin A, B, D and C9 petroleum resin (iodine value: 131I) are selected₂100g), Luteger TA100 resin (a copolymerization product of phenol with an unsaturated aromatic C9/C10 fraction, iodine number: 64I₂100g), hydrogenated C9 resin (iodine value: 18I₂100g) to carry out application performance test comparison, the rubber composition mixing process flow is as follows:

step one, mixing: NS460 and BR are firstly thin-pass plasticated on an open mill according to the mass ratio in Table 1 and mixed evenly. And then adding the blend rubber into a Germany Haake torque rheometer with the set temperature of 120 ℃ for banburying for 30s at the rotating speed of 60rpm, adding the functionalized resin, the zinc oxide, the stearic acid, the antioxidant RD, the antioxidant 4020 and the paraffin 9332F according to the mass ratio, banburying for 180s, adding the white carbon black and the silane coupling agent Si-69 for three times, and banburying for 180 s. And (4) discharging the glue, wherein the glue discharging temperature is controlled within 140 ℃.

And (4) thinly passing through an open mill for three times, and discharging to obtain the first-stage master batch.

Second step, two-stage mixing: adding a first section of masterbatch, sulfur, an accelerator NS and an accelerator DPG into a Germany Haake torque rheometer with the temperature set to be 90 ℃ and the rotating speed set to be 55rpm according to the mass ratio for banburying for 90s, and controlling the temperature to be below 100 ℃ for rubber discharge. Then, the mixture was kneaded by tumbling on an open mill, and after passing through the roll for 5 times, the mixture was discharged to prepare a rubber composition.

The application performance test method of the rubber composition comprises the following steps:

and (3) measuring the vulcanization performance: the method comprises the following steps of (1) determining the vulcanization performance of the rubber material by using a high-speed rail detection instrument, namely a model M-3000A no-rotor rheometer manufactured by the company Limited and referring to GB/T16584-;

and (3) testing mechanical properties: and (3) carrying out mechanical property test on the sizing material by using an AL-7000S type tensile machine of a high-speed rail detection instrument company Limited and referring to GB/T528-2009.

Hardness of vulcanized rubber: hardness of the rubber compound was measured by GBT531.1-2008 using an LX-A type hardness tester manufactured by Jiangsu Bright bead test machines Co.

Thermal oxygen aging test: and performing thermo-oxidative aging test on the rubber material by adopting a GT-7017-NL type aging box and referring to GB/T3512-2001.

And (3) cutting resistance test: the compounds were tested for cut resistance according to GB/T529-1999.

And DMA test: and testing the vulcanized rubber by dynamic mechanical analysis, wherein the test conditions are as follows: the test mode is a tensile mode, the dynamic strain is 0.25%, the static strain is 1%, and the heating rate is 3K/min. The larger the tan delta value at 0 ℃, the better the anti-wet skid capability; the smaller the value of tan delta at 60 ℃, the lower the heat build-up value of the belt compound.

TABLE 1 formulation (unit: parts by weight)

The test results are shown in Table 2.

Table 2.

From the data of table 2, the following conclusions can be drawn:

1) mooney viscosity has a certain correlation with processability, and when the Mooney viscosity is too high, the processability is deviated. From the mooney viscosity data, it can be seen that the mooney viscosity of composition A, B, D, I is less than H, which indicates that phenolic hydroxyl groups introduced in petroleum resin can interact with silica through polarity, so as to improve dispersion of silica, reduce filler network, and improve processability, wherein cardanol content of B is more, and processability is optimal. Compared with the I, the cardanol has better compatibility with a rubber matrix and better improvement on the processing performance because of containing long-chain alkane; the reason why the Mooney processability of the composition J is good is that the compatibility of the structure itself with the rubber is good.

2) The rheological data can reflect the vulcanization efficiency of the rubber compound, and the rheological data shows that the composition H consumes the sulfur crosslinking complex due to the fact that the composition H contains more double bonds, so that the T90 is the longest, the vulcanization efficiency is reduced, and the process cost is increased. Composition J, however, has a minimum double bond content and essentially no sulfur is consumed from the compound, thereby minimizing cure time. The double bond content of the resin is controlled by the using amount of cardanol in the composition A, B, D, I, so that excessive consumption of a sulfur cross-linked complex can be avoided, and higher vulcanization efficiency is ensured. However, phenol is more acidic than cardanol, and the acidic group inhibits the generation of radicals, and suppresses the generation of di-radical sulfur at the initial stage of vulcanization, and also retards vulcanization. Thus, composition A, D exhibited a higher cure efficiency than composition I, less double bonds in composition B, and a slightly shorter cure time.

3) The mechanical property can reflect the strength of the rubber material, and the double bonds in the composition H can influence the crosslinking of the rubber composition due to the existence of the double bonds, so that the tensile strength and the stress at definite elongation of vulcanized rubber are low, and the service performance and the service life of the tire are influenced. Wherein composition J has the least double bond content and higher tensile strength. The composition A, B, D, I regulates and controls the mechanical property of vulcanized rubber by regulating and controlling the double bond content, so that the rubber material has higher mechanical strength, wherein the composition B has less double bond content and slightly higher strength. Composition A, D, I was substantially equivalent in strength.

4) The cut resistance test data can intuitively reflect the tear resistance of the rubber composition. According to the cutting resistance data, the cutting resistance can be improved after the double bonds of the resin are adjusted through cardanol; when the crosslinking density of the vulcanized rubber is higher, more crosslinking points are available, the molecular chain flexibility is poor, and the cutting resistance is poor; when the crosslinking density is smaller, the strength is lower, and the cutting resistance is also poorer, so that the proper double bond content of the resin ensures that the rubber has proper crosslinking density and strength, and the cutting resistance of the rubber can be improved. The double bond content of the resin is not adjusted properly in the compositions H and J, the cutting resistance of the rubber is not obviously improved, the composition A, B, D, F has better performance, and the composition D has the best cutting resistance due to the proper double bond content and the excellent compatibility with the rubber.

5) In a dynamic performance test, a loss factor (tan delta) can be used for representing the dynamic viscoelastic performance of a rubber material, generally, a tan delta value at 0 ℃ represents the wet skid resistance of the tread rubber, and the higher the value is, the better the wet skid resistance of the tread rubber is; meanwhile, the tan delta value at 60 ℃ represents the rolling resistance of the tread rubber, and the higher the resin is, the larger the surface heat generation is, and the poorer the performance is. DMA data shows that the composition J has poor action with rubber due to less double bond content, and meanwhile, the benzene series part is replaced by a cycloalkane structure, so that the rigidity is weakened, the composition J has lower glass transition temperature, shows lower tan delta value at 0 ℃, and has the worst wet skid resistance; hydroxyl is introduced into the composition A, B, D, I, so that the dispersion of the filler is improved, the compatibility with rubber is better, the glass transition temperature of the rubber is increased, and therefore, the wet skid resistance effect is better than that of the composition H; cardanol is more compatible with rubber matrix than phenol because it contains long chain olefins, so composition a has better wet skid and heat generation than composition I. The cardanol content of the composition B is high, so that the composition B has better wet skid resistance compared with the composition A; the compatibility between the main chain of the composition D and rubber is better, the wet skid resistance of the composition D is excellent, the heat generation is lower, and the composition D has the optimal dynamic mechanical property, so that the safety performance of a tire is improved, and meanwhile, the lower oil consumption is ensured.

Therefore, by combining mechanical properties, rheological data, Mooney, cutting resistance tests and dynamic property tests, the resin with poor wet skid resistance caused by less double bonds, poor action with rubber and less rigid structure of the pure hydrogenated resin can be known; the strength and the vulcanization efficiency of the rubber compound are reduced due to excessive double bonds of the composition H; compared with phenol modified resin, the cardanol modified resin has small acidity and better compatibility with rubber, so that the cardanol modified resin has higher vulcanization efficiency, better wet skid resistance and lower heat generation. According to the invention, the double bonds of the resin are selectively modified by cardanol, so that the double bond content of the resin is moderate, a sulfur cross-linked complex is not consumed in a large amount, a certain acting force between the resin and rubber is ensured, the compatibility is better, and the comprehensive performance is excellent; in addition, the reason why the dynamic property of the composition D is better than that of A, B is that the composition D adopts C5/C9 copolymer resin which has an aliphatic hydrocarbon structure and a benzene structure, so that the composition D has better compatibility with rubber and enables the rubber filler to be dispersed more uniformly.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.