CN105622844A - Modified terpene resin and preparation method thereof - Google Patents
Modified terpene resin and preparation method thereof Download PDFInfo
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- CN105622844A CN105622844A CN201610171756.1A CN201610171756A CN105622844A CN 105622844 A CN105622844 A CN 105622844A CN 201610171756 A CN201610171756 A CN 201610171756A CN 105622844 A CN105622844 A CN 105622844A
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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
- C08F236/10—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 with vinyl-aromatic monomers
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- 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
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Abstract
The invention discloses modified terpene resin and a preparation method thereof, and relates to the technical field of preparation of forestry chemical products. Directed at defects of terpene resin and existing modified terpene resin in the market at present, the modified terpene resin is a polymer obtained by copolymerization of three monomeric substances including 20wt%-80wt% of pinene, 10wt%-50wt% of cis-1, 3-pentadiene and 5wt%-40wt% of alpha-methylstyrene under the action of a catalyst and an antioxidant. The modified terpene resin is characterized by low color and luster, high softening point, low wax cloud point, good compatibility, excellent anti-aging performance and the like. When applied to the adhesives, the modified terpene resin can substantially improve the use performance of adhesives, and not only increases the initial adhesion, but also apparently improves the persistent adhesion and peeling strength. The preparation method disclosed by the invention is easy, the reaction condition is easy to control, the production cost is low, the polymerization yield is high, and the industrial production is facilitated.
Description
(1) technical field
The invention belongs to forest chemical product preparing technical field, it relates to a kind of modified terpene resin and its preparation method, specifically disclose and a kind of prepare the method for modified terpene resin by raw material of cis-1,3-pentadiene, alpha-methyl styrene and turps.
(2) background technology
Terpine resin, also known as polyterpene or pinene resin. It mainly utilizes the ��-pinene of turps, beta-pinene, phellandrene etc., under not kirschner catalyst action, and a series of simple linear polymers from liquid to solid obtained through cationoid polymerisation. Because having the excellent chemical properties such as excellent physicals and acid and alkali-resistance such as nontoxic, hydrophobic, non-crystallizable, electrical isolation, increasing be sticky, it is soluble in aromatic hydrocarbon and vegetables oil, it is a kind of excellent tackifier, it has been applied to the fields such as rubber, plastics, ink, coating, weaving, tackiness agent, pressure sensitive adhesive, cable, color printing, paint, packaging, slushing oil, foodstuffs industry. But terpine resin ageing resistance is poor, tackiness agent tack can be improved although being used in tackiness agent, but the peeling force of tackiness agent and hold glutinous power and decrease, and the polarity synthetic elastomer consistency such as EVA, SIS, acrylate is not good; Along with industrial automatization is more and more higher, requiring more high to Adhensive performance, terpine resin can not meet the requirement of high-quality tackiness agent; Though now commercially having some modified resin products to list, but such modified terpene resin preparation method is often more numerous and diverse, kind and specification are still little, and quality is not high, and performance still can not meet the requirement of high-quality tackiness agent.
(3) summary of the invention
The present invention is directed to the above-mentioned deficiency existing for existing modified terpene resin in terpine resin and existing market, it is provided that a kind of have superior aging resistance energy, the modified terpene resin of excellent physical and chemical performance and its preparation method.
The concrete technical scheme of the present invention is as follows:
A kind of modified terpene resin, it is by firpene, cis-1,3-pentadiene, alpha-methyl styrene three kinds of monomers polymkeric substance that copolymerization obtains under the effect of catalyzer and oxidation inhibitor; The weight percent of its modified terpene resin three kinds of monomer formulas consists of: firpene 20-80wt%, cis-1,3-pentadiene 10-50wt%, alpha-methyl styrene 5-40wt%.
Described firpene is turps;
Described catalyzer is aluminum chloride, and its add-on is the 4-5wt% of three kinds of total monomer weights;
Described antioxidant is selected from pentaerythritol ester kind antioxidant or 5-tertiary butyl-4-hydroxy-2-methylbenzene thioether kind antioxidant, and its add-on is three kinds of total monomer weight 0.0001-0.001wt%.
The weight percent composition of three kinds of described monomer formulas is preferably: firpene 40-70wt%, cis-1,3-pentadiene 25-40wt%, alpha-methyl styrene 5-25wt%.
The preparation method of a kind of modified terpene resin as claimed in claim 1, comprise following operation steps: (1) throw material: add in proportion in measuring container firpene 20-80wt%, cis-1,3-pentadiene 10-50wt%, alpha-methyl styrene 5-40wt% tri-kinds of monomeric substances and mix; Catalyzer, oxidation inhibitor, solvent are joined in reaction vessel. (2) polyreaction: under agitation, slowly dripped in reaction vessel by mixed three kinds of monomeric substances in 30-45 minute and carry out polyreaction, polymerization pressure is normal pressure, control polymeric reaction temperature-10-10 DEG C, polymerization reaction time 2-8 hour; (3) washing and distillation: the mixed solution after polyreaction being completed, washs with 70-90 DEG C of water, divides anhydrate phase, distillating recovering solvent and oligopolymer, obtain modified terpene resin.
Described firpene is turps;
Described catalyzer is aluminum chloride, and its add-on is the 4-5wt% of three kinds of total monomer weights;
The one that described oxidation inhibitor is selected from pentaerythritol ester kind antioxidant or 5-tertiary butyl-4-hydroxy-2-methylbenzene thioether kind antioxidant, its add-on is the 0.0001-0.001wt% of three kinds of total monomer weights;
Described solvent is selected from the one of toluene or dimethylbenzene, and its add-on is 0.8-1 times of three kinds of total monomer weights.
The weight percent composition of three kinds of described monomer formulas is preferably: firpene 40-70wt%, cis-1,3-pentadiene 25-40wt%, alpha-methyl styrene 5-25wt%.
Control polymeric reaction temperature is preferably-5-5 DEG C, and control polymerization reaction time is preferably 4-6 hour.
Described modified terpene resin preparation method, is divided into batch production technique or continuous production processes two kinds in suitability for industrialized production.
Described batch production technique, its production process is: be that material is thrown in gap through mixed monomeric substance, then through the process such as polymerization, hydrolysis, distillation, completes the manufacture of one batch of modified terpene resin.
Described continuous production processes, its production process is: be continuous dosing through mixed monomeric substance, solvent and catalyzer, for add continuously, adopt DCS system automatically to control polymerization, washing, still-process, it is achieved the automatic continuous production of modified terpene resin on whole production line.
Modified terpene resin is widely used in adhesive industry, has good consistency with thermoplastic elastomer, the natural rubber such as SIS, SEBS, APP, is applicable to prepare the tackiness agent taking SIS, polyolefine and elastomerics thereof as base-material.
The useful effect of the present invention is: this modified terpene resin is the polymkeric substance obtained by firpene, cis-1,3-pentadiene, alpha-methyl styrene copolymerization, and it has, and color and luster is low, softening temperature height, the low consistency of wax cloud point are good, the excellent feature of ageing resistance. This modification terpene resin is applied to tackiness agent, can significantly improve the use properties of tackiness agent, and not only tack increases, and holds viscosity and stripping strength also significantly strengthens. Especially the increasing of ��-methylstyrenemonomer proportioning, contributes to the consistency of polarity and the polarity elastomerics improving modified terpene resin; The increasing of cis-1,3-pentadiene monomer ratio, contributes to improving peeling force and the hold tack of tackiness agent. Thus add the range of application of terpine resin, meet the needs of modern industry automatization. Preparation method of the present invention is simple, and reaction conditions is easy to control, and production cost is low, polymerization receipts rate height, is easy to carry out suitability for industrialized production.
(4) embodiment
Following examples are for illustration of the present invention, but are not used for limiting the scope of the invention.
Embodiment 1:
Add in separating funnel turps 70g, cis-1,3-pentadiene 25g, alpha-methyl styrene 5g tri-kinds of monomeric substances and mix; In the 500ml there-necked flask of drying, add aluminum trichloride catalyst 5g, pentaerythritol ester oxidation inhibitor 0.0005g, toluene 100g respectively, three kinds of monomeric substances will be housed and mixed even separating funnel and flask prop up a mouthful abutting joint; Under magnetic agitation and normal pressure, 40 minutes used times slowly dripped mixed three kinds of monomeric substances and enter and carry out polyreaction in there-necked flask, control polyreaction bath temperature 0 DEG C, 6 hours polyreaction used times; Mixed solution after polyreaction being completed, washs with 80 DEG C of water, divides phase of anhydrating, distillating recovering solvent and oligopolymer, obtaining faint yellow solid modified terpene resin 86.5g (production code member 1#), this product color is 5 after testing, and softening temperature is 100 DEG C.
Embodiment 2:
Add in separating funnel turps 50g, cis-1,3-pentadiene 25g, alpha-methyl styrene 25g tri-kinds of monomeric substances and mix; In the 500ml there-necked flask of drying, add aluminum trichloride catalyst 5g, pentaerythritol ester oxidation inhibitor 0.0005g, toluene 100g respectively, three kinds of monomeric substances will be housed and mixed even separating funnel and flask prop up a mouthful abutting joint; Under magnetic agitation and normal pressure, 40 minutes used times slowly dripped mixed three kinds of monomeric substances and enter and carry out polyreaction in there-necked flask, control polyreaction bath temperature 0 DEG C, 6 hours polyreaction used times; Mixed solution after polyreaction being completed, washs with 80 DEG C of water, divides anhydrate phase, distillating recovering solvent and oligopolymer, obtains faint yellow solid modified terpene resin 87g (production code member 2#), and this product color is 4 after testing, and softening temperature is 99 DEG C.
Embodiment 3:
Add in separating funnel turps 40g, cis-1,3-pentadiene 40g, alpha-methyl styrene 20g tri-kinds of monomeric substances and mix; In the 500ml there-necked flask of drying, add aluminum trichloride catalyst 5g, pentaerythritol ester oxidation inhibitor 0.0005g, toluene 100g respectively, three kinds of monomeric substances will be housed and mixed even separating funnel and flask prop up a mouthful abutting joint; Under magnetic agitation and normal pressure, 40 minutes used times slowly dripped mixed three kinds of monomeric substances and enter and carry out polyreaction in there-necked flask, control polyreaction bath temperature 0 DEG C, 6 hours polyreaction used times; Mixed solution after polyreaction being completed, washs with 80 DEG C of water, divides phase of anhydrating, distillating recovering solvent and oligopolymer, obtaining faint yellow solid modified terpene resin 87.5g (production code member 3#), this product color is 5 after testing, and softening temperature is 101 DEG C.
Embodiment 4:
Add in separating funnel turps 70g, cis-1,3-pentadiene 25g, alpha-methyl styrene 5g tri-kinds of monomeric substances and mix; In the 500ml there-necked flask of drying, add aluminum trichloride catalyst 4g, antimony trichloride catalyst 1g, pentaerythritol ester oxidation inhibitor 0.0005g, toluene 100g respectively, three kinds of monomeric substances will be housed and mixed even separating funnel and flask prop up a mouthful abutting joint; Under magnetic agitation and normal pressure, 30 minutes used times slowly dripped mixed three kinds of monomeric substances and enter and carry out polyreaction in there-necked flask, control polyreaction bath temperature-10 DEG C, 8 hours polyreaction used times; Mixed solution after polyreaction being completed, washs with 70 DEG C of water, divides anhydrate phase, distillating recovering solvent and oligopolymer, obtains faint yellow solid modified terpene resin 86.5g, and this product color is 5 after testing, and softening temperature is 100 DEG C.
Embodiment 5:
Add in separating funnel turps 50g, cis-1,3-pentadiene 25g, alpha-methyl styrene 25g tri-kinds of monomeric substances and mix; In the 500ml there-necked flask of drying, add aluminum trichloride catalyst 5g, 5-tertiary butyl-4-hydroxy-2-methylbenzene thioether oxidation inhibitor 0.0005g, toluene 100g respectively, three kinds of monomeric substances will be housed and mixed even separating funnel and flask prop up a mouthful abutting joint; Under magnetic agitation and normal pressure, 40 minutes used times slowly dripped mixed three kinds of monomeric substances and enter and carry out polyreaction in there-necked flask, control polyreaction bath temperature 5 DEG C, 4 hours polyreaction used times; Mixed solution after polyreaction being completed, washs with 80 DEG C of water, divides anhydrate phase, distillating recovering solvent and oligopolymer, obtains faint yellow solid modified terpene resin 87g, and this product color is 5 after testing, and softening temperature is 99 DEG C.
Embodiment 6:
Add in separating funnel turps 40g, cis-1,3-pentadiene 40g, alpha-methyl styrene 20g tri-kinds of monomeric substances and mix; In the 500ml there-necked flask of drying, add aluminum trichloride catalyst 5g, pentaerythritol ester oxidation inhibitor 0.0005g, dimethylbenzene 100g respectively, three kinds of monomeric substances will be housed and mixed even separating funnel and flask prop up a mouthful abutting joint; Under magnetic agitation and normal pressure, 40 minutes used times slowly dripped mixed three kinds of monomeric substances and enter and carry out polyreaction in there-necked flask, control polyreaction bath temperature 10 DEG C, 2 hours polyreaction used times; Mixed solution after polyreaction being completed, washs with 80 DEG C of water, divides phase of anhydrating, distillating recovering solvent and oligopolymer, obtaining faint yellow solid modified terpene resin 87.5g (production code member 3#), this product color is 5 after testing, and softening temperature is 101 DEG C.
Embodiment 7:
Add in separating funnel turps 40g, cis-1,3-pentadiene 40g, alpha-methyl styrene 20g tri-kinds of monomeric substances and mix; In the 500ml there-necked flask of drying, add aluminum trichloride catalyst 4g, pentaerythritol ester oxidation inhibitor 0.001g, toluene 100g respectively, three kinds of monomeric substances will be housed and mixed even separating funnel and flask prop up a mouthful abutting joint; Under magnetic agitation and normal pressure, 45 minutes used times slowly dripped mixed three kinds of monomeric substances and enter and carry out polyreaction in there-necked flask, control polyreaction bath temperature 6 DEG C, 3 hours polyreaction used times; Mixed solution after polyreaction being completed, washs with 90 DEG C of water, divides anhydrate phase, distillating recovering solvent and oligopolymer, obtains faint yellow solid modified terpene resin 87g, and this product color is 5 after testing, and softening temperature is 101 DEG C.
Embodiment 8:
Add in separating funnel turps 40g, cis-1,3-pentadiene 40g, alpha-methyl styrene 20g tri-kinds of monomeric substances and mix; In the 500ml there-necked flask of drying, add aluminum trichloride catalyst 5g, pentaerythritol ester oxidation inhibitor 0.0001g, toluene 80g respectively, three kinds of monomeric substances will be housed and mixed even separating funnel and flask prop up a mouthful abutting joint; Under magnetic agitation and normal pressure, 45 minutes used times slowly dripped mixed three kinds of monomeric substances and enter and carry out polyreaction in there-necked flask, control polyreaction bath temperature-5 DEG C, 6 hours polyreaction used times; Mixed solution after polyreaction being completed, washs with 80 DEG C of water, divides anhydrate phase, distillating recovering solvent and oligopolymer, obtains faint yellow solid modified terpene resin 87.5g, and this product color is 5 after testing, and softening temperature is 101 DEG C.
Embodiment 9:
Add in separating funnel turps 40g, cis-1,3-pentadiene 40g, alpha-methyl styrene 20g tri-kinds of monomeric substances and mix; In the 500ml there-necked flask of drying, add aluminum trichloride catalyst 5g, pentaerythritol ester oxidation inhibitor 0.0005g, toluene 90g respectively, three kinds of monomeric substances will be housed and mixed even separating funnel and flask prop up a mouthful abutting joint; Under magnetic agitation and normal pressure, 45 minutes used times slowly dripped mixed three kinds of monomeric substances and enter and carry out polyreaction in there-necked flask, control polyreaction bath temperature 5 DEG C, 4 hours polyreaction used times; Mixed solution after polyreaction being completed, washs with 80 DEG C of water, divides anhydrate phase, distillating recovering solvent and oligopolymer, obtains faint yellow solid modified terpene resin 87.2g, and this product color is 5 after testing, and softening temperature is 101 DEG C.
Embodiment 10 modified terpene resin continuous production processes main points:
Start logical icy salt solution to be lowered the temperature by toluene solvant in polymeric kettle, with pump by turps, cis-1,3-pentadiene and alpha-methyl styrene three kinds of monomer mixture material, input is added with in 50% liquid level polymeric kettle of catalyzer, solvent continuously, polyreaction is carried out under stirring, polymeric kettle liquid level 80%, adds solvent and catalyzer simultaneously continuously, and maintenance liquid level is put and expected washing workshop section; Washing workshop section is the settling tank composition of three groups of series connection band static mixers, and hot water and polymer material enter static mixer and be hydrolyzed to settling tank, wash, clarify draining, complete washing continuously. Washed material enters distillation tower continuously and deviates from solvent and low-grade polymer, desolvation and low-grade polymer, and material modified terpene resin enters tablets press and carries out granulation packaging.
Polymerization, wash and distill DCS system on whole production line and automatically control. It is aggregated in the setting given refrigerating duty parameter of temperature of reaction and automatically regulates monomer catalyzer charging capacity; Washing setting layering automatic liquid surface control water discharging valve aperture; Distill and require that setting distillation temperature regulates heat and charging amount automatically according to product softening temperature. Alleviating staff labor intensity, improve Working environment, equipment runs and improves 30% efficiency, it is to increase stable prod output and quality.
Comparative example 1 two kinds of monomer polymerization reactions:
Add in separating funnel turps 60g, cis-1,3-pentadiene 40g bis-kinds of monomeric substances and mix; In the 500ml there-necked flask of drying, add aluminum trichloride catalyst 5g, pentaerythritol ester oxidation inhibitor 0.0005g, toluene 90g respectively, two kinds of monomeric substances will be housed and mixed even separating funnel and flask prop up a mouthful abutting joint; Under magnetic agitation and normal pressure, 45 minutes used times slowly dripped mixed two kinds of monomeric substances and enter and carry out polyreaction in there-necked flask, control polyreaction bath temperature 5 DEG C, 4 hours polyreaction used times; Mixed solution after polyreaction being completed, washs with 80 DEG C of water, divides anhydrate phase, distillating recovering solvent and oligopolymer, obtains faint yellow solid modified terpene resin 85g (production code member 5#), and this product color is 5 after testing, and softening temperature is 99 DEG C.
The preparation of comparative example 2 terpine resin reference product only has a kind of monomer polymerization reactions of turps:
In the 500ml there-necked flask of drying, add aluminum trichloride catalyst 5g, pentaerythritol ester oxidation inhibitor 0.0005g, toluene 90g respectively, separating funnel and flask that 100g turps is housed are propped up a mouthful abutting joint; Under magnetic agitation and normal pressure, 45 minutes used times slowly dripped 100g turps and enter and carry out polyreaction in there-necked flask, control polyreaction bath temperature 5 DEG C, 4 hours polyreaction used times; Mixed solution after polyreaction being completed, washs with 80 DEG C of water, divides phase of anhydrating, distillating recovering solvent and oligopolymer, obtain faint yellow solid terpine resin 85g (production code member 5# is reference product), this product color is 5 after testing, and softening temperature is 98 DEG C.
Product 1#, 2#, 3#, 4# compare with reference product 5# performance test:
Faint yellow solid modified terpene resin 1#, 2#, 3# embodiment 1,2,3 obtained, with terpine resin 4#, 5# reference product that comparative example 1, comparative example 2 obtain, carries out performance test and comparison.
Determining of wax cloud point: EVA, terpine resin, Microcrystalline Wax are mixed according to mass ratio 30:45:25, be heated to clear in test tube, stirs cooling, and temperature when record mixture occurs vaporific is as wax cloud point. The low consistency of wax cloud point is good.
Determining of thermostability: be placed in baking oven by terpine resin, at 200 DEG C, aging 3h takes out and surveys its color and luster. It is excellent that color and luster changes little ageing resistance.
Tack test method is pressed: GB/T4852-2002
Hold adhesive test method by GB/T4851-1998
180 peeling strength test method: GB/T2792-1998
Test proportioning: natural rubber: terpine resin: oxidation inhibitor: toluene=22.4:24.1:0.8:87.8
Monomer ratio A:B:C=turps: cis-1,3-pentadiene: alpha-methyl styrene
Under test result is shown in:
Carry out the performance test results from upper table 1#-5# product can draw: 1#2#3# product (three kinds of monomer ratios) is compared with 5# reference product (a kind of monomer ratio), wax cloud point obviously reduces, illustrating that modified terpene resin is than comparison terpine resin, its polarity is greatly improved, polarity elastomer compatibility has had obvious improvement; Color change little (color of the first five product sample of test is 5) in thermal stability determination, illustrate that modified terpene resin is than comparison terpine resin, its ageing resistance is improved, not only tack increases, and holds viscosity and stripping strength two indexs significantly strengthen.
1#2#3# product is (two kinds of monomer ratios compared with 4# reference product, lack C monomer), wax cloud point also has obvious reduction, the modified terpene resin of the modified terpene resin of three kinds of monomer ratios than two kinds of monomer ratios is described, its polarity is greatly improved, polarity elastomer compatibility has had obvious improvement; Color change little (color of the first five product sample of test is 5) in thermal stability determination, the modified terpene resin of the modified terpene resin of three kinds of monomer ratios than two kinds of monomer ratios is described, its ageing resistance is improved, not only tack increases, and holds viscosity and stripping strength two indexs significantly strengthen.
Analyze known further: modified terpene resin 2# product (C25%) is compared with 3# product (C20%), 1# product (C5%) product, wax cloud point is minimum is 67, the increasing of ��-methylstyrenemonomer proportioning is described, contributes to the consistency of polarity and the polarity elastomerics improving modified terpene resin. And modified terpene resin 3# product (B40%) is compared with 1# product (B25%), 2# product (B25%), hold viscosity and stripping strength two indexs the highest, it is respectively 29.5 and 0.97, illustrate cis-1, the increasing of 3-pentadiene monomer ratio, contributes to improving peeling force and the hold tack of tackiness agent.
Claims (10)
1. a modified terpene resin, it is characterised in that: it is by firpene, cis-1,3-pentadiene, alpha-methyl styrene three kinds of monomers polymkeric substance that copolymerization obtains under the effect of catalyzer and oxidation inhibitor; The weight percent of its modified terpene resin three kinds of monomer formulas consists of: firpene 20-80wt%, cis-1,3-pentadiene 10-50wt%, alpha-methyl styrene 5-40wt%.
2. a kind of modified terpene resin according to claim 1, it is characterised in that: described firpene is turps.
3. a kind of modified terpene resin according to claim 1, it is characterised in that: described catalyzer is aluminum chloride, and its add-on is the 4-5wt% of three kinds of total monomer weights; The one that described oxidation inhibitor is selected from pentaerythritol ester kind antioxidant or 5-tertiary butyl-4-hydroxy-2-methylbenzene thioether kind antioxidant, its add-on is the 0.0001-0.001wt% of three kinds of total monomer weights.
4. according to any one modified terpene resin described in claim 1-3, it is characterized in that: the weight percent of three kinds of described monomer formulas consists of: firpene 40-70wt%, cis-1,3-pentadiene 25-40wt%, alpha-methyl styrene 5-25wt%.
5. a preparation method for modified terpene resin as claimed in claim 1, comprises following operation steps:
(1) throw material: add in proportion in measuring container firpene 20-80wt%, cis-1,3-pentadiene 10-50wt%, alpha-methyl styrene 5-40wt% tri-kinds of monomeric substances and mix; Catalyzer, oxidation inhibitor, solvent are joined in reaction vessel;
(2) polyreaction: under agitation, slowly dripped in reaction vessel by mixed three kinds of monomeric substances in 30-45 minute and carry out polyreaction, polymerization pressure is normal pressure, control polymeric reaction temperature-10-10 DEG C, polymerization reaction time 2-8 hour;
(3) washing and distillation: the mixed solution after polyreaction being completed, washs with 70-90 DEG C of water, divides anhydrate phase, distillating recovering solvent and oligopolymer, obtain modified terpene resin.
6. the preparation method of a kind of modified terpene resin according to claim 5, it is characterised in that: the firpene described in step (1) is turps; Described catalyzer is selected from aluminum chloride, butter of antimony, and its add-on is the 4-5wt% of three kinds of total monomer weights; The one that described oxidation inhibitor is selected from pentaerythritol ester kind antioxidant or 5-tertiary butyl-4-hydroxy-2-methylbenzene thioether kind antioxidant, its add-on is the 0.0001-0.001wt% of three kinds of total monomer weights; Described solvent is selected from toluene or the one of dimethylbenzene or chlorine benzyl, and its add-on is 0.8-1 times of three kinds of total monomer weights.
7. the preparation method of a kind of modified terpene resin according to claim 5, it is characterized in that: the weight percent of three kinds of monomer formulas described in step (1) consists of: firpene 40-70wt%, cis-1,3-pentadiene 25-40wt%, alpha-methyl styrene 5-25wt%.
8. the preparation method of a kind of modified terpene resin according to claim 5, it is characterised in that: the polymeric reaction temperature described in step (2) is controlled to-5-5 DEG C, and polymerization reaction time is controlled to 4-6 hour.
9. the preparation method of a kind of modified terpene resin according to claim 5, it is characterised in that: described preparation method, is divided into batch production technique or continuous production processes two kinds in suitability for industrialized production.
10. the preparation method of a kind of modified terpene resin according to claim 8, it is characterized in that: described batch production technique, its production process is: through mixed monomeric substance be gap throw material, then through processes such as polymerization, hydrolysis, distillations, the manufacture of one batch of modified terpene resin is completed; Described continuous production processes, its production process is: be continuous dosing through mixed monomeric substance, solvent and catalyzer, for add continuously, adopt DCS system automatically to control polymerization, washing, still-process, it is achieved the automatic continuous production of modified terpene resin on whole production line.
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| US3299170A (en) * | 1963-10-10 | 1967-01-17 | Schenectady Chemical | Alpha pinene copolymer as a tackifier for polymers |
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