CN105504165A - Production method of modified coumarone resin - Google Patents
Production method of modified coumarone resin Download PDFInfo
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- CN105504165A CN105504165A CN201610039005.4A CN201610039005A CN105504165A CN 105504165 A CN105504165 A CN 105504165A CN 201610039005 A CN201610039005 A CN 201610039005A CN 105504165 A CN105504165 A CN 105504165A
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- production method
- cracking
- coumarone indene
- indene resin
- polymerization
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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
- C08F244/00—Coumarone-indene copolymers
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a production method of modified coumarone resin. The production method comprises the following steps: (1) carrying out cracking on 2-cyanoethyl-5-norbornene-2-carboxaldehyde at 150-210 DEG C in a vacuum kettle; (2) after the cracking, mixing cracking products obtained from the kettle bottom, pre-fractioned carbolic oil and heavy benzol and ethylene cracked C9 fractions with a boiling point of 180 DEG C in a raw material tank; (3) after the mixing, adding a catalyst into a polymerization washing tank, carrying out prepolymerization at 50 DEG C for 0.5 hour, removing the catalyst by virtue of calcium hydroxide, transferring products into a reaction kettle, adding boron trifluoride, heating to 140 DEG C, and carrying out secondary polymerization for 2 hours; and (4) after the secondary polymerization, transferring the products into a distillation still, carrying out reduced pressure distillation at 250 DEG C, and condensing by virtue of a resin cooling disc, so as to obtain the modified coumarone resin. The softening, tackifying and reinforcing effects of the coumarone resin produced by virtue of the production method are good.
Description
Technical field
The present invention relates to a kind of resin, particularly relate to a kind of production method of modification coumarone indene resin.
Background technology
Coumarone indene resin is the multipolymer of cumarone and indenes, is a kind of thermoplastic petroleum resin, by passing through process to cumarone contained in 160 ~ 165 DEG C of cuts of coal tar and indenes, refine, then obtains through catalyzed copolymerization.Coumarone indene resin has good water tolerance, resistance to acids and bases, and be dissolved in hydrochloric ether, ester class, ketone, ethers equal solvent, electrical insulating property, ageing resistance, thermotolerance are good; Good with rubber compatibility, be solvent based adhesion promoter, due to the advantage in performance numerous so, deeply welcomed by the people for a long time.Cross the multiplex natural rosin resins of no-bonder or indenes olefine resin, price is high, and source is unstable.Coumarone indene resin adds in rubber, can play the effects such as softening, reinforcement, thickening, dispersion.The dominant position of binding agent has been occupied at present in industries such as rubber.Along with the continuous increase of synthetic rubber consumption, also increasing to the demand of coumarone indene resin, but coumarone indene resin is worth from the spirit fraction of coal tar, and the scale avenged due to plum blossom and raw material are all restricted, so the output of coumarone indene resin is also affected.Therefore, its output be improved, other raw materials of Development and Production coumarone indene resin are significant.
Summary of the invention
For above-mentioned prior art Problems existing, the invention provides a kind of production method of modification coumarone indene resin, raw material is easy to be easy to get, and the coumarone indene resin produced is softening, thickening, and reinforcing effect is all good.
According to above-mentioned prior art Problems existing, the technical scheme that the present invention takes is: a kind of production method of modification coumarone indene resin, is characterized in that, comprise the steps:
1) 2-cyanoethyl-5-Norbornene-2-carboxaldehyde carries out cracking 5-8h in vacuum still under 150-210 DEG C of condition;
2) carbolic oil after getting split product at the bottom of still, fore-running after cracking and heavy benzol and boiling point mix in raw material tank at the cracking of ethylene C9 cut of 180 DEG C;
3) add catalyzer and carry out prepolymerization in polymerization rinse bath after mixing, prepolymerization temperature is 50 DEG C, and the time is 0.5 hour, goes to reactor and add boron trifluoride to be warming up to 140 DEG C and to carry out after polymerization after calcium hydroxide Removal of catalyst, and the time is 2 hours;
4) after after polymerization terminates, enter still kettle and carry out underpressure distillation, still kettle vacuum tightness is-0.09MPa, and temperature is 250 DEG C, carries out condensation namely obtain modification coumarone indene resin after combustion through resin coolship.
Step 2) in the weight ratio of split product, carbolic oil, heavy benzol and C9 cut at the bottom of still be (6 ~ 8): 2:3:2.
Step 2) described in catalyzer be the sulfuric acid of 93%, add-on is the 0.1%-0.2% of total weight of material.
Step 2) in boron trifluoride add-on be the 0.2%-0.25% of total weight of material.
Modification coumarone indene resin prepared by the present invention, softening, thickening, and reinforcing effect is all good, softening point range is at 80 ~ 90 DEG C, and excellent corrosion resistance, electrical insulating property, stretch-proof, tear resistance and ageing resistance are good.The key technical indexes: relative density 1.05 ~ 1.15, second-order transition temperature 56 DEG C, specific refractory power 1.60-1.65, pH value 5 ~ 9, iodine number 23-39gI
2/ 100g; In addition, 2-cyanoethyl-5-Norbornene-2-carboxaldehyde distills in vacuum cracking process and rectifying cut out can be used for imidacloprid synthesis, in other words, in Provado building-up process, the by product at the bottom of still after the cracking of 2-cyanoethyl-5-Norbornene-2-carboxaldehyde, also raw material used in the present invention, considerably increases the source of coumarone indene resin raw material.
Embodiment
Embodiment 1
A production method for modification coumarone indene resin, comprises the steps:
1) 2-cyanoethyl-5-Norbornene-2-carboxaldehyde to carry out in vacuum still cracking 5 hours under 150-210 DEG C of condition;
2) carbolic oil after getting split product at the bottom of still, fore-running after cracking and heavy benzol, with boiling point 180 DEG C cracking of ethylene C9 cut mix with raw material tank, the weight ratio of split product, carbolic oil, heavy benzol and C9 cut is 6:2:3:2;
3) sulfuric acid adding 93% after mixing in polymerization rinse bath carries out prepolymerization, and prepolymerization temperature is 50 DEG C, and the time is 0.5 hour, goes to reactor and add boron trifluoride to be warming up to 140 DEG C and to carry out after polymerization after calcium hydroxide Removal of catalyst, and the time is 2 hours; The sulphuric acid of 93% is 0.1% of total weight of material; Boron trifluoride add-on is 0.2% of total weight of material.
4) after after polymerization terminates, enter still kettle and carry out underpressure distillation, still kettle vacuum tightness is-0.09MPa, and temperature is 250 DEG C, carries out condensation namely obtain modification coumarone indene resin after combustion through resin coolship.
Embodiment 2
A production method for modification coumarone indene resin, comprises the steps:
1) 2-cyanoethyl-5-Norbornene-2-carboxaldehyde to carry out in vacuum still cracking 8 hours under 150-210 DEG C of condition;
2) carbolic oil after getting split product at the bottom of still, fore-running after cracking and heavy benzol, with boiling point 180 DEG C cracking of ethylene C9 cut mix with raw material tank, the weight ratio of split product, carbolic oil, heavy benzol and C9 cut is 8:2:3:2;
3) sulfuric acid adding 93% after mixing in polymerization rinse bath carries out prepolymerization, and prepolymerization temperature is 50 DEG C, and the time is 0.5 hour, goes to reactor and add boron trifluoride to be warming up to 140 DEG C and to carry out after polymerization after calcium hydroxide Removal of catalyst, and the time is 2 hours; The sulphuric acid of 93% is 0.2% of total weight of material; Boron trifluoride add-on is 0.25% of total weight of material.
4) after after polymerization terminates, enter still kettle and carry out underpressure distillation, still kettle vacuum tightness is-0.09MPa, and temperature is 250 DEG C, carries out condensation namely obtain modification coumarone indene resin after combustion through resin coolship.
Modification coumarone indene resin achievement data prepared by embodiment 1 and embodiment 2 is as shown in table 1:
Modification coumarone indene resin achievement data prepared by table 1 embodiment 1 and embodiment 2
| Index name | Embodiment 1 | Detection method |
| Colourity | ≤ 3 5 9 | By standard color solution |
| Softening temperature | 80～90℃ | Ring and ball method |
| PH value | 5～9 | PH meter |
| Moisture | ≤0.3% | |
| Ash content | ≤0.15% |
Embodiment 3
Rubber A is prepared: natural rubber 9 parts, cis-butadiene cement 2.8 parts, butadiene-styrene rubber 11 parts, captax are 0.82 part, accelerant C E is 0.2, prepared by EVA4 part, high-phenylethylene 3.2 parts, fine particle calcium carbonate 6.0 parts, glycol ether 0.5 part, embodiment 1 coumarone indene resin 0.8 part, 1.0 parts, zinc oxide, stearic acid 0.45 part, white carbon black 7 parts, 0.8 part, machine oil according to the proportioning of following weight part, 4 parts, sulphur, adopts conventional fabrication process to make.
Embodiment 4
Rubber B is prepared: natural rubber 12 parts, cis-butadiene cement 4.2 parts, butadiene-styrene rubber 13 parts, captax are 0.82 part, accelerant C E is 0.2, prepared by EVA8 part, high-phenylethylene 4.3 parts, fine particle calcium carbonate 7.5 parts, glycol ether 1.0 parts, embodiment 2 coumarone indene resin 1.2 parts, 2.0 parts, zinc oxide, stearic acid 0.6 part, white carbon black 10 parts, 1.2 parts, machine oil according to the proportioning of following weight part, 7 parts, sulphur, adopts conventional fabrication process to make.
Embodiment 5
Prepare rubber C according to the proportioning of following weight part: natural rubber 12 parts, cis-butadiene cement 4.2 parts, butadiene-styrene rubber 13 parts, captax are 0.82 part, accelerant C E is 0.2, EVA8 part, high-phenylethylene 4.3 parts, fine particle calcium carbonate 7.5 parts, glycol ether 1.0 parts, 2.0 parts, zinc oxide, stearic acid 0.6 part, white carbon black 10 parts, 1.2 parts, machine oil, 7 parts, sulphur, adopts conventional fabrication process to make.
Rubber A-C prepared by embodiment 3-5 carries out performance test:
(1) carry out the mensuration of 300% tensile modulus, tensile strength, elongation according to GB528-82 standard, result is as shown in table 2:
The measurement result of table 2300% tensile modulus, tensile strength, elongation
| 300% tensile modulus (MPa) | Tensile strength (MPa) | Elongation (%) | |
| Rubber A | 8.1 | 12.3 | 708 |
| Rubber B | 8.0 | 11.1 | 715 |
| Rubber C | 13.5 | 17.8 | 409 |
As can be seen from Table 2,300% tensile modulus and the tensile strength of rubber A and rubber B are all low than rubber C, and elongation, then far away higher than rubber C, describes coumarone indene resin prepared by the present invention and has good bating effect.
(2) carry out the mensuration of shore hardness, tear strength and setafter break according to GB531-83 and GB529-81 standard, result is as shown in table 3:
The measurement result of table 3 shore hardness, tear strength and setafter break
| Shore hardness (A) | Tear strength (N/cm) | Setafter break (%) | |
| Rubber A | 82 | 988 | 23 |
| Rubber B | 83 | 987 | 24 |
| Rubber C | 65 | 710 | 14 |
As can be seen from Table 3, the shore hardness of rubber A and rubber B, tear strength and setafter break are all high than rubber C, describe coumarone indene resin prepared by the present invention and have good reinforcing effect.
(3) in 100 DEG C of warm airs, carry out the senile experiment of 48 hours according to GB-1512-83, aging resistance result is as shown in table 4:
Table 4 aging resistance experimental result
| Tear strength (N/cm) | Tensile yield (%) | Aging coefficient | |
| Rubber A | 967 | 401 | 0.911 |
| Rubber B | 969 | 402 | 0.918 |
| Rubber C | 608 | 299 | 0.531 |
As can be seen from Table 4, with the addition of performance data after overaging of coumarone indene resin prepared by the present invention and aging before be more or less the same, be obviously better than un-added rubber C.
Claims (4)
1. a production method for modification coumarone indene resin, is characterized in that, comprises the steps:
1) 2-cyanoethyl-5-Norbornene-2-carboxaldehyde carries out cracking 5-8h in vacuum still under 150-210 DEG C of condition;
2) carbolic oil after getting split product at the bottom of still, fore-running after cracking and heavy benzol and boiling point mix in raw material tank at the cracking of ethylene C9 cut of 180 DEG C;
3) add catalyzer and carry out prepolymerization in polymerization rinse bath after mixing, prepolymerization temperature is 50 DEG C, and the time is 0.5 hour, goes to reactor and add boron trifluoride to be warming up to 140 DEG C and to carry out after polymerization after calcium hydroxide Removal of catalyst, and the time is 2 hours;
4) after after polymerization terminates, enter still kettle and carry out underpressure distillation, still kettle vacuum tightness is-0.09MPa, and temperature is 250 DEG C, carries out condensation namely obtain modification coumarone indene resin after combustion through resin coolship.
2. the production method of modification coumarone indene resin according to claim 1, is characterized in that, step 2) in the weight ratio of split product, heavy benzol and C9 cut be 2:3:2.
3. the production method of modification coumarone indene resin according to claim 1, is characterized in that, step 2) described in catalyzer be the sulfuric acid of 93%, add-on is 0.1% of total weight of material.
4. the production method of modification coumarone indene resin according to claim 1, is characterized in that, step 2) in boron trifluoride add-on be 0.2% of total weight of material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610039005.4A CN105504165A (en) | 2016-01-20 | 2016-01-20 | Production method of modified coumarone resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610039005.4A CN105504165A (en) | 2016-01-20 | 2016-01-20 | Production method of modified coumarone resin |
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| CN105504165A true CN105504165A (en) | 2016-04-20 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201610039005.4A Withdrawn CN105504165A (en) | 2016-01-20 | 2016-01-20 | Production method of modified coumarone resin |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110128243A (en) * | 2019-06-05 | 2019-08-16 | 恒河材料科技股份有限公司 | A method of propylene glycol in weight alcohol waste liquid is recycled using extraction |
| CN111909316A (en) * | 2020-08-06 | 2020-11-10 | 抚顺齐隆化工有限公司 | Preparation method of coumarone resin for high-carbon-residue carbon fibers |
-
2016
- 2016-01-20 CN CN201610039005.4A patent/CN105504165A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110128243A (en) * | 2019-06-05 | 2019-08-16 | 恒河材料科技股份有限公司 | A method of propylene glycol in weight alcohol waste liquid is recycled using extraction |
| CN111909316A (en) * | 2020-08-06 | 2020-11-10 | 抚顺齐隆化工有限公司 | Preparation method of coumarone resin for high-carbon-residue carbon fibers |
| CN111909316B (en) * | 2020-08-06 | 2022-05-10 | 抚顺齐隆化工有限公司 | Preparation method of coumarone resin for high-carbon-residue carbon fibers |
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Application publication date: 20160420 |