CN111454399A - Light-colored high-softening-point modified carene resin and preparation method thereof - Google Patents
Light-colored high-softening-point modified carene resin and preparation method thereof Download PDFInfo
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- CN111454399A CN111454399A CN202010363312.4A CN202010363312A CN111454399A CN 111454399 A CN111454399 A CN 111454399A CN 202010363312 A CN202010363312 A CN 202010363312A CN 111454399 A CN111454399 A CN 111454399A
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- carene
- resin
- softening
- light
- isoprene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/08—Isoprene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J145/00—Adhesives based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Adhesives based on derivatives of such polymers
Abstract
A light-color high-softening-point modified carene resin is a polymer obtained by copolymerizing a 3-carene crude product and isoprene under the action of a solvent, a catalyst and an antioxidant, and comprises the following components in percentage by mass: 50-70% of 3-carene crude product and 30-50% of isoprene. During preparation, toluene, pentaerythritol ester antioxidant and anhydrous aluminum trichloride are added into a container for reaction, and then 3-carene crude product and isoprene are added and stirred for reaction to obtain reaction liquid; and washing the reaction solution, separating a water phase, and distilling to recover the solvent and the oligomer to obtain the light-color high-softening-point modified carene resin. The preparation method has easily controlled reaction conditions and high polymerization yield, can prepare tackifying resin with better quality, is widely applied to the adhesive industry, has good compatibility with thermoplastic elastomers and natural rubber such as SIS, SEBS, APP and the like, and is suitable for preparing adhesives taking SIS, polyolefin and the elastomers thereof as base materials.
Description
Technical Field
The invention relates to deep processing of chemical resin, in particular to light-color high-softening-point modified carene resin and a preparation method thereof.
Background
The terpene resin is a yellow transparent brittle thermoplastic solid, has excellent physical properties such as non-toxicity, hydrophobicity, non-crystallization, electrical insulation, tackifying and the like, and excellent chemical properties such as acid-base resistance, ageing resistance and the like, is easily soluble in aromatic hydrocarbon and vegetable oil, is an excellent tackifier, and is widely applied to the fields of rubber, plastics, printing ink, coatings, textiles, adhesives, pressure-sensitive adhesives, cables, color printing, paints, packaging, antirust oil, food industry and the like.
The method comprises the steps of taking alpha-pinene or β -pinene of turpentine as a raw material, carrying out cationic polymerization under the action of a Friedel's catalyst to obtain the terpene resin, wherein the pinene raw material is expensive with the reduction of ecological environment protection and the yield of turpentine year by year, and finally increasing the production cost of the terpene resin.
3-carene, the chemical name of which is 3, 7, 7-trimethylbicyclo (4.1.0) -3-heptene, is a chiral source compound containing a ternary ring structure in a small number of natural world, mainly exists in various turpentine oil, is particularly rich in Indian palustre turpentine oil and European red turpentine oil, the utilization of the turpentine oil is developed around a-pinene and β -pinene for a long time, and the research personnel begin to pay extensive attention and attention to the improvement of the fine utilization value of the 3-carene-rich turpentine oil.
Disclosure of Invention
The invention aims to provide a light-colored high-softening-point modified carene resin which takes a 3-carene crude product as a raw material to prepare the modified carene resin and broadens the application of the 3-carene, and the modified carene resin has light color and high softening point, and has good adhesive force, oxidation resistance and thermal stability, and a preparation method thereof.
The light-color high-softening-point modified carene resin is a polymer obtained by copolymerizing a crude product of 3-carene and isoprene under the action of a solvent, a catalyst and an antioxidant, and comprises the following components in percentage by mass: 50-70% of 3-carene crude product and 30-50% of isoprene.
The crude product of 3-carene consists of 3-carene, limonene, β -pinene,% myrcene and p-cymene, and the mass percentages of the crude product of 3-carene, limonene, β -pinene, 2.27%, myrcene, 1.06%, p-cymene and the balance of 3-carene are 19.5%, β -pinene, 2.90% and p-cymene.
The solvent is toluene, and the addition amount of the toluene is 80-100% of the total mass of the 3-carene crude product and the isoprene.
The catalyst is anhydrous aluminum trichloride, and the addition amount of the anhydrous aluminum trichloride is 4-8% of the total mass of the 3-carene crude product and the isoprene.
The antioxidant is pentaerythritol ester antioxidant, and the addition amount of the antioxidant is 0.0005-0.001% of the total mass of the 3-carene crude product and the isoprene.
The preparation method of the light-color high-softening-point modified carene resin comprises the following steps:
1) adding toluene, pentaerythritol ester antioxidant and anhydrous aluminum trichloride into a container for reaction, adding a crude product of 3-carene and isoprene, and stirring for reaction to obtain a reaction solution;
in the step 1), the reaction temperature can be-10 ℃; the adding time can be 30-50 min, and the stirring reaction time can be 3-8 h.
2) And washing the reaction solution, separating a water phase, and distilling to recover the solvent and the oligomer to obtain the light-color high-softening-point modified carene resin.
In the step 2), the washing can be carried out by using water at the temperature of 80-90 ℃.
The light-color high-softening-point modified carene resin product obtained by the invention has the color (Garder by the Gardner method) of less than or equal to 6, the acid value (mgKOH/g) of less than or equal to 1.0, toluene insoluble substance (w/w%) -of less than or equal to 0.05, and the softening point (by a ring-and-ball method, the temperature is higher than or equal to 130), and can be dissolved in aromatic hydrocarbon, acetic ester and the like.
Compared with the prior art, the invention has the following outstanding beneficial effects:
the formula and the process conditions of the invention are optimized, and the total polymerization yield reaches more than 80 percent after the polymer is washed and the solvent, the residual raw materials and the oligomers are removed; the preparation method has the advantages of easily controlled reaction conditions and high polymerization yield, can prepare tackifying resin with better quality, is widely applied to the adhesive industry, has good compatibility with thermoplastic elastomers and natural rubber such as SIS, SEBS, APP and the like, and is suitable for preparing adhesives taking SIS, polyolefin and elastomers thereof as base materials.
Detailed Description
Specific examples are given below.
Example 1
1) Adding 120g of toluene and 6g of anhydrous aluminum trichloride into a dry 500ml four-neck flask, controlling the temperature at-10 ℃, slowly adding 75g of 3-carene crude product, 75g of isoprene and 0.0008g of pentaerythritol ester antioxidant into the reaction mixed solution, dripping for 30min, and stirring for reacting for 3 h;
2) and (2) washing the reaction mixed solution in the step (1) with water at 80 ℃, separating out a water phase, distilling and recovering the solvent and the oligomer to obtain 128g of light yellow solid modified carene resin, wherein the product has a color of 5 and a softening point of 139.0 ℃ by detection.
Example 2
1) Adding 130g of toluene and 8g of anhydrous aluminum trichloride into a dry 500ml four-neck flask, controlling the temperature at-5 ℃, slowly adding 82.5g of 3-carene crude product, 67.5g of isoprene and 0.0015g of pentaerythritol ester antioxidant into the reaction mixed solution, finishing dripping within 40min, and stirring for reacting for 4 h;
2) washing the reaction mixed solution in the step 1 with water at 90 ℃, separating out a water phase, and distilling to recover the solvent and the oligomer to obtain 124.3g of light yellow solid modified carene resin; the color of the product is detected to be 5, and the softening point is detected to be 136.5 ℃.
Example 3
1) Adding 150g of toluene and 10g of anhydrous aluminum trichloride into a dry 500ml four-neck flask, controlling the temperature at 0 ℃, slowly adding 90g of 3-carene crude product, 60g of isoprene and 0.0012g of pentaerythritol ester antioxidant into the reaction mixed solution, finishing dropping for 35min, and stirring for reacting for 5.5 h;
2) washing the reaction mixed solution in the step 1 with water at 85 ℃, separating out a water phase, and distilling to recover the solvent and the oligomer to obtain 120.2g of light yellow solid modified carene resin; the color of the product is detected to be 4, and the softening point is 132.5 ℃.
Example 4
1) Adding 150g of toluene and 12g of anhydrous aluminum trichloride into a dry 500ml four-neck flask, controlling the temperature at 5 ℃, slowly adding 97.5g of crude 3-carene, 52.5g of isoprene and 0.001g of pentaerythritol ester antioxidant into the reaction mixed solution, finishing dropping in 50min, and stirring for reacting for 7 h;
2) washing the reaction mixed solution in the step 1 with water at 85 ℃, separating out a water phase, and distilling to recover the solvent and the oligomer to obtain 121.6g of light yellow solid modified carene resin; the color of the product is detected to be 5, and the softening point is detected to be 134.0 ℃.
Example 5
1) Adding 150g of toluene and 12g of anhydrous aluminum trichloride into a dry 500ml four-neck flask, controlling the temperature at 10 ℃, slowly adding 105g of 3-carene crude product, 45g of isoprene and 0.001g of pentaerythritol ester antioxidant into the reaction mixed solution, finishing dripping for 40min, and stirring for reacting for 8 h;
2) washing the reaction mixed solution in the step 1 with water at 85 ℃, separating out a water phase, and distilling to recover the solvent and the oligomer to obtain 124.4g of light yellow solid modified carene resin; the color of the product is detected to be 5, and the softening point is 131.5 ℃.
The invention prepares the modified carene resin by copolymerizing the 3-carene crude product and isoprene, widens the application range of the 3-carene, and has the advantages of easy control of reaction conditions, high polymerization yield, light color of the resin and high softening point.
Claims (10)
1. The light-color high-softening-point modified carene resin is characterized in that the light-color high-softening-point modified carene resin is a polymer obtained by copolymerizing a crude product of 3-carene and isoprene under the action of a solvent, a catalyst and an antioxidant, and the light-color high-softening-point modified carene resin comprises the following components in percentage by mass: 50-70% of 3-carene crude product and 30-50% of isoprene.
2. The light-colored high-softening-point modified carene resin of claim 1, wherein the crude 3-carene comprises 3-carene, limonene, β -pinene,% myrcene and p-cymene, and the mass percentages are limonene 19.5%, β -pinene 2.27%, myrcene 1.06%, p-cymene 2.90%, and the balance 3-carene.
3. The light-colored high-softening-point modified carene resin of claim 1, wherein the solvent is toluene, and the amount of toluene added is 80-100% of the total mass of the crude 3-carene and isoprene.
4. The light-colored high-softening-point modified carene resin of claim 1, wherein the catalyst is anhydrous aluminum trichloride added in an amount of 4-8% of the total mass of the crude 3-carene and isoprene.
5. The light-colored high-softening-point modified carene resin of claim 1, wherein the antioxidant is a pentaerythritol ester antioxidant added in an amount of 0.0005% to 0.001% of the total mass of 3-carene crude and isoprene.
6. The process for preparing light-colored high-softening-point modified carene resin of claim 1, characterized by comprising the steps of:
1) adding toluene, pentaerythritol ester antioxidant and anhydrous aluminum trichloride into a container for reaction, adding a crude product of 3-carene and isoprene, and stirring for reaction to obtain a reaction solution;
2) and washing the reaction solution, separating a water phase, and distilling to recover the solvent and the oligomer to obtain the light-color high-softening-point modified carene resin.
7. The method of preparing light-colored high-softening-point modified carene resin of claim 6, wherein in step 1), the temperature of the reaction is-10 to 10 ℃.
8. The method of claim 6, wherein in step 1), the addition time is 30-50 min.
9. The method for preparing light-colored high-softening-point modified carene resin of claim 6, wherein in the step 1), the stirring reaction time is 3-8 h.
10. The method of claim 6, wherein in step 2), the washing is performed with water at 80-90 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010363312.4A CN111454399A (en) | 2020-04-30 | 2020-04-30 | Light-colored high-softening-point modified carene resin and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010363312.4A CN111454399A (en) | 2020-04-30 | 2020-04-30 | Light-colored high-softening-point modified carene resin and preparation method thereof |
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| CN111454399A true CN111454399A (en) | 2020-07-28 |
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| CN202010363312.4A Pending CN111454399A (en) | 2020-04-30 | 2020-04-30 | Light-colored high-softening-point modified carene resin and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040158003A1 (en) * | 2003-02-06 | 2004-08-12 | Arizona Chemical Company | Terpene resin-and hydrocarbon resin-based surfactants and aqueous dispersion of tackifier resins |
| CN1709927A (en) * | 2005-07-08 | 2005-12-21 | 广西大学 | Method for preparing colorless terpene resin |
| CN101891862A (en) * | 2010-08-18 | 2010-11-24 | 赣州泰普化学有限公司 | Modified terpene resin and preparation method thereof |
| CN104151467A (en) * | 2014-08-21 | 2014-11-19 | 梧州市嘉盈树胶有限公司 | Preparation method of terpene resin |
-
2020
- 2020-04-30 CN CN202010363312.4A patent/CN111454399A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040158003A1 (en) * | 2003-02-06 | 2004-08-12 | Arizona Chemical Company | Terpene resin-and hydrocarbon resin-based surfactants and aqueous dispersion of tackifier resins |
| CN1709927A (en) * | 2005-07-08 | 2005-12-21 | 广西大学 | Method for preparing colorless terpene resin |
| CN101891862A (en) * | 2010-08-18 | 2010-11-24 | 赣州泰普化学有限公司 | Modified terpene resin and preparation method thereof |
| CN104151467A (en) * | 2014-08-21 | 2014-11-19 | 梧州市嘉盈树胶有限公司 | Preparation method of terpene resin |
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Application publication date: 20200728 |
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