CN102633919A - Terpene resin and preparation method thereof - Google Patents
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Abstract
The invention discloses a terpene resin and a preparation method thereof. The preparation method comprises steps as follows: terpene substances are used as a raw material, AlCl3 in the presence of an aromatic solvent is used as a main catalyst, and a cocatalyst is used in the reaction; polymerization is carried out at low temperature to prepare the crude terpene resin product; and the crude terpene resin product is washed and distilled under reduced pressure to obtain the terpene resin product. The cocatalyst is trimethylchlorosilane, triethylchlorosilane, tripropylchlorosilane or tributylchlorosilane, and accounts for 1-5% of the total mass of the terpene substance raw material; the main catalyst AlCl3 accounts for 4-12% of the total mass of the terpene substance raw material; the elemental chlorine content in the prepared terpene resin product is less than 100mg/kg, and the metallic aluminum content is less than 10mg/kg; the terpene resin product does not contain metallic antimony; and the residue level of the volatile solvent is less than 25mg/kg. The product reaches to the food level.
Description
Technical field
The present invention relates to a kind of terpine resin, especially can satisfy the preparation method of the terpine resin of food sanitation rank resin and deep processing and utilization technical requirements.
Background technology
Terpine resin is to be raw material with the terpene compound, the common name of the polymkeric substance that obtains through cationic polymerization.Common have terpine resin, α-Pai Xishuzhi, beta-pinene resin, a dipentene resin etc., also comprises modified terpene resin certainly, like terpenes styron, terpene phenolic resin, C5 modified terpene resin etc.
Terpine resin has nontoxic, and is hydrophobic, non-crystallizable; Electrical isolation; Good physicals and acid and alkali-resistances such as bonding force is strong, chemical property such as anti-aging is soluble in aromatic hydrocarbon and vegetables oil; Be a kind of good tackifier and the modifying agent of hot melt material, be widely used in fields such as rubber, plastics, printing ink, coating, weaving, tackiness agent, pressure sensitive adhesive, cable, color printing, paint, packing, slushing oil, foodstuffs industry.
With AlCl
3Be catalyzer, the technology for preparing terpine resin through cationoid polymerisation has very long history, and as far back as the twentieth century middle period, it is catalyzer that Roberts W. J. etc. has just proposed with Lewis acid, and polymerization prepares the process method of pinene resin.Patent US 2335912 contents that nineteen forty-three is issued are exactly with AlCl
3Be catalyzer, polymerizations such as beta-pinene, kautschin, terpinene generate the process method of terpine resin.Last century eight, the nineties, Deng Yunxiang etc. are to AlCl
3Be Primary Catalysts, SbCl
3Carry out systematic study for the α-Pai Xi polyreaction under the promotor condition, obtained good effect.Nowadays, be to be the industrial production that terpine resin is carried out on the basis basically with this technology.
, also there are a lot of improvable places in this technology, at first; This technology emulsion often occurs at washing step; Have a strong impact on the yield of product, in order to improve this situation, [US 2351786] such as Alfred L. Rummelsburg adopt HF to replace polyprotonic acid and monoterpene acting in conjunction; Polymerization obtains terpine resin, and this technology is obvious to reducing emulsification degree effect.In addition, itself there are many problems in the prepared terpine resin product of this technology.Be product meeting oxidation stain gradually in the standing storage process on the one hand, can thermotolerance, the weathering resistance of product be exerted an influence when serious; Be exactly on the other hand, adopt in this technology products made thereby the catalyst residue amount high, cause wherein cl content and heavy metal content severe overweight, limited it greatly such as the use in the fields such as food, medicine, health.To this problem, people improve terpine resin preparation technology.Wherein a kind of method is exactly that the lower terpine resin of quality is done hydrotreatment, and Zhou Yonghong etc. [CN 1422877] adopt the catalysis of nanometer nickel to make hydrogenated terpene resin, and Xiong Deyuan etc. [CN 1709927] adopt molecular sieve supported AlCl earlier
3Catalysis makes colorless terpene resin with the Pd/C catalytic hydrogenation again.A kind of in addition comparatively effective means improves catalyzer exactly, more commonly replaces Lewis acid commonly used with heteropolyacid at present.[CN 101555300A] such as Liu Zu Guang replaces Lewis acid with heteropolyacid is catalyzer, and cationoid polymerisation prepares a kind of terpine resin, and this technology is in that to improve aspect the native defect of product effect pretty good.A. B. Radbil etc. is with AlCl
3With the mixture of heteropolyacid be catalyzer, studied the polyreaction of α-Pai Xi, effect is better than single AlCl
3Catalysis.Yet these methods also have its weak point, though HF to helping to reduce the emulsification degree, itself toxicity is bigger, not too is fit to a large amount of the use.Though hydrogenant method effect aspect improvement terpine resin quality is distinguished, the production cost of hydrogenation reaction is higher, and is higher to the suitability for industrialized production equipment requirements.The method that replaces the Lewis acid catalyst with heteropolyacid catalyst; Though can reduce catalyst residue amount in the product, the production process of heteropolyacid own is loaded down with trivial details, and catalytic activity is good not as Lewis acid; In industrial production, can cause the product yield low, production cost is high.
Summary of the invention
The objective of the invention is to solve under the existing processing condition in the terpine resin product catalyzer remove difficult; Cause in the product cl content higher, heavy metal content exceeds standard, thereby causes products obtained therefrom can't satisfy the application demand of some high-end fields on the one hand; Be on the other hand when being applied to as raw material such as reprocessing processes such as hydrogenations; Cause a series of problems such as poisoning of catalyst and equipment corrosion easily, the invention provides a kind of terpine resin and preparation method thereof, catalyzer is removed easily; Do not contain heavy metal, product reaches food grade.
Technical scheme of the present invention is: a kind of preparation method of terpine resin is a raw material with the terpenoid substance, in the presence of aromatic solvent with AlCl
3Be Primary Catalysts; Be aided with promotor in the reaction again; Polymerization prepares the terpine resin bullion at low temperatures, and washing, underpressure distillation obtain the terpine resin product, and described promotor is any one in trimethylchlorosilane, chlorotriethyl silane, tripropyl chlorosilane or the tributyl chlorosilane; Add-on is 1 %～5 % of terpenoid substance raw material total mass, Primary Catalysts AlCl
3Add-on is 4 %～12 % of terpenoid substance raw material total mass, and elemental chlorine content is less than 100 mg/kg in the terpine resin product of preparation, and metallic aluminium content is less than 10 mg/kg, containing metal antimony not, and the volatile solvent residual quantity is less than 25 mg/kg.
Described terpenoid substance be in turps, α-Pai Xi, beta-pinene, folium eucalypti firpene 、 limonene, the kautschin any one or any several kinds arbitrarily than mixture.
Described turps is any in gum turpentine, steam-distilled(wood)turpentine, the sulfate turpentine.
Described aromatic solvent is any one in benzyl chloride, toluene or the YLENE.
Terpenoid substance is added dropwise in the aromatic solvent that contains Primary Catalysts and reacts, and after terpenoid substance drips, adds promotor again, and reacting initial temperature is-20～20 ℃, is reflected at≤carry out under 60 ℃ the low temperature, and the reaction times is 2～10 h.
Described underpressure distillation comprises the two-stage decompression still-process, is respectively: reclaim the rough vacuum underpressure distillation of 0.08 MPa～0.10 MPa of solvent, the high vacuum underpressure distillation of removing 0.3 kPa～2.0 KPa of oligopolymer.
Described washing is to use the acid solution washing earlier, re-uses the alkaline solution washing, at last with hot wash.
The terpine resin that adopts the preparation method of described terpine resin to obtain, elemental chlorine content is less than 100 mg/kg in the terpine resin product, and metallic aluminium content is less than 10 mg/kg, containing metal antimony not, and the volatile solvent residual quantity is less than 25 mg/kg.
The terpine resin that the preparation method of described employing terpine resin obtains is in Application in Food Processing.
Beneficial effect:
1. the present invention has given up used promotor SbCl in original technology
3, eliminated the influence of heavy metal Sb to product quality;
2. to adopt trialkyl chlorosilane (being abbreviated as TASC) be promotor in the present invention, solved residual catalyst and the molecular resin difficult technologies difficult problem of dissociating, and solved in original technology washing process simultaneously and occurred emulsification easily and cause the layering problem of difficult.Adopt technology method of the present invention not only can significantly reduce catalyst residue amount in the product, also can reduce loss of material simultaneously, improve the product yield;
3. the product quality for preparing of the present invention is high, does not especially contain poisonous metal elements such as Antimony Metal 99.65& 99.96, and cl content can reach below 10 of existing Industrial products chlorine output; Below one of good reached percentage, promptly quality has improved 10～100 times, and cl content is less than 100 mg/kg (custom was called ppm) in the past in the terpine resin product that makes with Technology of the present invention; Metal A l content is less than 10 mg/kg (being scaled massfraction is 0.001 %); Containing metal Sb not, the volatile solvent residual quantity is less than 25 mg/kg, and quality product can satisfy U.S. FDA foodstuff additive standard fully to terpine resin quality (FDA; 172.615; 1994: arsenic≤3 mg/kg, heavy metal≤0.004 %, lead≤3 mg/kg; Q3C impurity: solvent residual amount: toluene: PDE (day contact amount)≤8.9 mg/ days) requirement.Can satisfy the quality demand of food, health, deep processing and utilization sector applications such as (as preparing hydrogenated terpene resin etc.) fully;
4. technological method of the present invention can use current production devices basically when production application, need not improve existing installation, is easy to be extended and applied.
Embodiment
With terpene compounds such as turps, α-Pai Xi, beta-pinene 、 limonene (PC 560 or limonene), kautschins is raw material, and aromatic hydrocarbons such as toluene are solvent, AlCl
3Be Primary Catalysts, trialkyl chlorosilane (being abbreviated as TASC) is a promotor, and polymerization prepares terpine resin at low temperatures, and the concrete operations step is following:
The exsiccant there-necked flask that whisking appliance, TM and constant pressure funnel are housed is placed in the cryogenic thermostat reactive bath technique, in flask, adds a certain amount of solvent, and reaction raw materials is added in the constant pressure funnel; When treating in the flask that temperature is reduced to the required starting temperature of reaction, take by weighing a certain amount of Primary Catalysts fast, and in mortar, grind pulping, change in the reaction flask with little solvent; Open and stir, begin at the uniform velocity dropwise reaction raw material, temperature begins to rise in the reaction flask, when temperature descends, can add Primary Catalysts; After raw material dropwises, add promotor, continue to react to the object time; After reaction finishes, reaction unit is shifted out the cryogenic thermostat reactive bath technique together, add a certain amount of 5 % aqueous hydrochloric acids, continue to stir 10～30 min, reaction solution is changed in the separating funnel; Divide sub-cloud water liquid, add a certain amount of 5 % alkali aqueous solutions washing once, divide sub-cloud water liquid, supernatant liquid adds the hot wash about 80 ℃, is neutral until washings; The gained supernatant liquid obtains the terpine resin product through underpressure distillation.
In the aforesaid method, solvent load is 0.5: 1～1: 1 with the raw materials quality ratio; The Primary Catalysts consumption is 4 %～12 % of raw materials quality; The promotor consumption is 1 %～5 % of raw materials quality, and described promotor is any one in trimethylchlorosilane, chlorotriethyl silane, tripropyl chlorosilane or the tributyl chlorosilane; Reacting initial temperature is-20 ℃～20 ℃, and the temperature control in the reaction process is below 60 ℃; Reaction times is 2 h～10h.
Preferred scheme is: turps is raw material, and toluene is solvent, Primary Catalysts AlCl
3Consumption is 8 % of raw materials quality, and adds at twice, and promotor TASC consumption is 2 % of raw materials quality; Reacting initial temperature is-5 ℃, and the raw material dropping time is controlled at about 1 h, coreaction 6 h; Through overpickling-alkali cleaning-washing, two step underpressure distillation obtain the terpine resin product again.Products obtained therefrom is carried out cl content and Determination of Residual Organic Solvents detects, find that wherein cl content is about 50 mg/kg, toluene level less than 20 mg/kg, do not contain other volatile matter.
The analysis of cl content in the terpine resin product:
Instrument: ZWK-2001 microcomputer sulphur chlorine analyzers, Jiangyan City analytical instrument company of high section.
Parameter: furnace temperature: 750 ℃ of stable sections, 850 ℃ of burning zones, 650 ℃ of vaporization sections; N
2: 200 mL/min～230 mL/min, O
2: 80 mL/min～100 mL/min; Bias voltage: 260 mV～280 mV, integrating resistor: 200 Ω～2 k Ω, gain: 2400.
Reagent: electrolytic solution: the mixed solution of 700 mL glacial acetic acids and 300 mL redistilled waters; Standard specimen: cl content is measured with reference material 50 ppm, 100 ppm, Research Institute of Petro-Chemical Engineering.
The analytical sample preparation method: solid sample is pulverized the back direct injection.
Method for quantitatively determining: measure standard specimen, computing system transformation efficiency, general transformation efficiency need just can carry out sample determination greater than 70 %; Analytic sample, according to the micro-coulometric titration principle, system calculates cl content in the sample automatically.
The analysis of volatile component content in the terpine resin product:
Instrument: gas chromatograph GC-2014, day island proper Tianjin company.
Parameter: chromatographic column: Rtx-50 (50 % dimethyl-/50 % phenylbenzene ZGK 5,30 m * 0.25 mm * 0.25 μ m); Detector: FID; Injector temperature: 250 ℃, detector temperature: 250 ℃; Sample size: 5 μ L; Splitting ratio: 50: 1; Temperature programming:
Reagent: solvent hexane (chromatographically pure, Nanjing Chemistry Reagent Co., Ltd.); External standard toluene (chromatographically pure, Nanjing Chemistry Reagent Co., Ltd.)
Stratographic analysis preparation method of sample: contrast liquid: take by weighing the toluene of a series of different contents, place 10 mL volumetric flasks respectively, add normal hexane to scale marks; Sample: accurately take by weighing the resin sample (being accurate to 0.001 g) of 0.5 g～1.0 g, add a small amount of normal hexane, fully change in the 10 mL volumetric flasks after the dissolving, add normal hexane to scale marks.
Method for quantitatively determining: the analysis of control article are X-coordinate with the toluene concentration, and peak area is that ordinate zou is made typical curve; Analytic sample utilizes typical curve, adopts toluene level in the external standard method calculation sample.Data processing software: functional activities of the body fluid phase chromatogram workpiece station, island.
Only need change external standard when measuring other organic solvent gets final product.
Embodiment 1
TM, whisking appliance and constant pressure funnel are installed on the there-necked flask respectively, and flask is placed the cryogenic thermostat reactive bath technique; 100 mL toluene are added in the there-necked flask, open refrigeration and reach-6 ℃ to the interior temperature of bottle; Take by weighing the anhydrous AlCl of 8.2 g rapidly
3, and in mortar, grind pulping with 30 mL toluene, change in the lump in the reaction flask, a temperature is-5 ℃ in this moment bottle; 144.9 g turps (are wherein contained α-Pai Xi 75 %wt; Beta-pinene 15 %wt) mixture with 16.1 g folium eucalypti firpenes (wherein containing α-Pai Xi 96 %wt) adds in the constant pressure funnel; Open cock, begin to drip raw material, it is about 100 d/min that speed is dripped in control; Temperature rises rapidly in the bottle, is up to 9 ℃; When treating that a bottle interior reaction temperature begins to descend, use with quadrat method and add catalyzer, comprising AlCl
35.0 g, toluene 30 mL, a temperature begins to descend after rising to 12 ℃ of mxm.s once more in the bottle; Raw material dropwises behind about 1 h, adds 3.5 g promotor trimethylchlorosilanes (TMSC); After reacting 6 h, the entire reaction device is shifted out from low-temp reaction is bathed, add about 150 mL, 5 % aqueous hydrochloric acids, continue to stir 15 min, change separating funnel over to; Divide sub-cloud water liquid, add about 150 mL, 5 % KOH aqueous solution, shake well, standing demix divides sub-cloud liquid; With 400 mL hot water repeated washing supernatant liquids 5 times; Last gained supernatant liquid reclaims toluene through the rough vacuum underpressure distillation earlier, and wherein vacuum tightness is 0.095 MPa, and outlet temperature is 170 ℃, reclaims and obtains toluene and unreacted turps 108.2 g; After the cooling, adopt molecular distillation to remove oligopolymer, vacuum tightness is 0.8 kPa, distills that temperature is 260 ℃ at the bottom of the final still.Finally obtain terpine resin product 86 g, (during calculated yield, raw materials quality is as the criterion with original add-on yield 53.4 %; Do not deduct the terebinthine quality that recovery can utilize again; So apparent resin yield is on the low side, down together), 89 ℃ of softening temperatures; Cl content 70.3 mg/kg, toluene residual quantity 20.3 mg/kg.
Embodiment 2
Raw material is 160.5 g turps (wherein containing α-Pai Xi 75 %, beta-pinene 15 %), 5 ℃ of initial reaction temperatures, and promotor consumption 5.2 g, all the other technologies are with embodiment 1.Finally must reclaim toluene and turps mixture 140 g, terpine resin product 86 g, yield 59.7 %, 91 ℃ of softening temperatures, cl content 53. 8 mg/kg in the product, toluene residual quantity 17.5 mg/kg.
Embodiment 3
Raw material is the mixture of 80 g turps and 82.5 g folium eucalypti firpenes, 0 ℃ of initial reaction temperature, and all the other technologies are with embodiment 1.Finally must reclaim toluene and unreacted turps 131.2 g, terpine resin product 86.5 g, yield 53.2%, 84 ℃ of product softening temperatures, cl content 82.0 mg/kg in the product, toluene residual quantity 19.9 mg/kg.
Embodiment 4
Raw material is 160 g turps (wherein containing α-Pai Xi 75 %, beta-pinene 15 %), reacting initial temperature-4 ℃, and all the other technologies are with embodiment 1.Final toluene and the unreacted turps 141.7g of reclaiming obtains terpine resin product 87g, yield 54.4 %, 87 ℃ of product softening temperatures, cl content 99.45 mg/kg in the product, toluene residual quantity 19.7 mg/kg.
Embodiment 5
Raw material is that all the other technologies of 160 g turps (wherein containing α-Pai Xi 75 %, beta-pinene 15 %) are with embodiment 1.Reclaim toluene and unreacted turps 118g at last, get terpine resin product 95g, yield 59.4%, 87 ℃ of product softening temperatures, cl content 52.45mg/kg in the product, toluene residual quantity 21.6 mg/kg.
Embodiment 6
Raw material 160 g turps (wherein containing α-Pai Xi 75 %, beta-pinene 15 %), 3 ℃ of starting temperatures, all the other technologies are with embodiment 1.The result reclaims toluene and unreacted turps totally 184 g, terpine resin product 86 g, yield 53.8 %, 99 ℃ of product softening temperatures, cl content 77.8 mg/kg in the product, toluene residual quantity 18.4 mg/kg.
Embodiment 7
Raw material 160 g limonenes (content 95 %wt), starting temperature-20 ℃, promotor is the tripropyl chlorosilane, and solvent is a benzyl chloride, and all the other technologies are with embodiment 1.The result reclaims benzyl chloride and Wei anti-Ying limonene totally 129.7 g, terpine resin product 81.7 g, yield 51.1 %, 86 ℃ of product softening temperatures, cl content 74.1 mg/kg in the product, toluene residual quantity 19.4 mg/kg.
Embodiment 8
Raw material 160 g kautschins (Qi Zhong Han limonene 44 %wt, α-terpinene 13%, terpinolene 26%), 15 ℃ of starting temperatures, promotor is the tributyl chlorosilane, all the other technologies are with embodiment 1.The result reclaims toluene and the unreacted kautschin is total to 193.7g, gets terpine resin product 82 g, yield 51.3 %, 81 ℃ of product softening temperatures, cl content 99.8 mg/kg in the product, toluene residual quantity 22.1 mg/kg.
The salient features of each embodiment products obtained therefrom gathers sees table 1:
Table 1 embodiment product salient features analytical results summary sheet
| Embodiment | Raw material g | Softening temperature ℃ | Cl content mg/kg | Toluene level mg/kg | Al content mg/kg | Sb content mg/kg |
| 1 | 160.0 | 89 | 70.3 | 20.3 | Do not detect | Do not detect |
| 2 | 160.5 | 91 | 53.8 | 17.5 | Do not detect | Do not detect |
| 3 | 162.5 | 84 | 82.0 | 19.9 | 2.7 | Do not detect |
| 4 | 160.0 | 87 | 99.5 | 19.7 | 3.3 | Do not detect |
| 5 | 160.0 | 87 | 52.5 | 21.6 | Do not detect | Do not detect |
| 6 | 160.0 | 99 | 77.8 | 18.4 | Do not detect | Do not detect |
| 7 | 160.0 | 86 | 74.1 | 19.4 | Do not detect | Do not detect |
| 8 | 160.0 | 81 | 99.8 | 22.1 | 3.4 | Do not detect |
| Commercially available article | — | 99 | 727.7 | 23.0 | 120.5 | 104.9 |
Can know by last table; The prepared product performance of technology of the present invention are good, be catalyzer, organic solvent or residual quantity of heavy metal all far below traditional technology resulting (commercially available) product, meet the index request (FDA of U.S. FDA to the terpine resin that uses as foodstuff additive; 172.615; 1994: arsenic≤3 mg/kg, heavy metal≤0.004%, lead≤3 mg/kg; Q3C impurity---solvent residual amount---toluene: PDE (day contact amount)≤8.9 mg/ days), can be applicable to high-end fields such as food, health fully.
Claims (8)
1. the preparation method of a terpine resin is a raw material with the terpenoid substance, in the presence of aromatic solvent with AlCl
3Be Primary Catalysts; Be aided with promotor in the reaction again, polymerization prepares the terpine resin bullion at low temperatures, and washing, underpressure distillation obtain the terpine resin product; It is characterized in that; Described promotor is any one in trimethylchlorosilane, chlorotriethyl silane, tripropyl chlorosilane or the tributyl chlorosilane, and add-on is 1 %～5 % of terpenoid substance raw material total mass, Primary Catalysts AlCl
3Add-on is 4 %～12 % of terpenoid substance raw material total mass, and elemental chlorine content is less than 100 mg/kg in the terpine resin product of preparation, and metallic aluminium content is less than 10 mg/kg, containing metal antimony not, and the volatile solvent residual quantity is less than 25 mg/kg.
2. the preparation method of terpine resin as claimed in claim 1 is characterized in that, described terpenoid substance be in turps, α-Pai Xi, beta-pinene, folium eucalypti firpene 、 limonene, the kautschin any one or any several kinds arbitrarily than mixture.
3. the preparation method of terpine resin as claimed in claim 2 is characterized in that, described turps is any in gum turpentine, steam-distilled(wood)turpentine, the sulfate turpentine.
4. the preparation method of terpine resin as claimed in claim 1 is characterized in that, described aromatic solvent is any one in benzyl chloride, toluene or the YLENE.
5. like the preparation method of the arbitrary described terpine resin of claim 1～4; It is characterized in that; Terpenoid substance is added dropwise in the aromatic solvent that contains Primary Catalysts and reacts, and after terpenoid substance drips, adds promotor again, and reacting initial temperature is-20～20 ℃; Be reflected at≤carry out under 60 ℃ the low temperature, the reaction times is 2～10 h.
6. like the preparation method of the arbitrary described terpine resin of claim 1～4; It is characterized in that; Described underpressure distillation comprises the two-stage decompression still-process, is respectively: reclaim the rough vacuum underpressure distillation of 0.08 MPa～0.10 MPa of solvent, the high vacuum underpressure distillation of removing 0.3 kPa～2.0 kPa of oligopolymer.
7. like the preparation method of the arbitrary described terpine resin of claim 1～4, it is characterized in that described washing is to use the acid solution washing earlier, re-uses the alkaline solution washing, at last with hot wash.
8. the terpine resin that adopts the preparation method of the described terpine resin of claim 1 to obtain; It is characterized in that elemental chlorine content is less than 100 mg/kg in the terpine resin product, metallic aluminium content is less than 10 mg/kg, containing metal antimony not; The volatile solvent residual quantity reaches food grade less than 25 mg/kg.
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| CN102898564A (en) * | 2012-11-01 | 2013-01-30 | 张道飘 | Method for preparing terpene resin |
| CN103450376A (en) * | 2013-08-29 | 2013-12-18 | 江西麻山化工有限公司 | Distillation process for synthetic resin production process |
| CN103450395A (en) * | 2013-08-28 | 2013-12-18 | 梧州市嘉盈树胶有限公司 | Preparation method of terpene resin |
| CN104211843A (en) * | 2014-08-14 | 2014-12-17 | 广西众昌树脂有限公司 | Preparation method of terpene resin |
| CN104877075A (en) * | 2015-05-19 | 2015-09-02 | 广西众昌树脂有限公司 | Method for producing terpene resin by taking turpentine as raw material |
| CN104910303A (en) * | 2015-05-27 | 2015-09-16 | 梧州市嘉盈树胶有限公司 | Method for preparing terpene resin by using dipentene as raw material |
| CN106519534A (en) * | 2016-12-05 | 2017-03-22 | 罗定市星光化工有限公司 | Production process of food-grade terpene resin |
| CN108017739A (en) * | 2017-12-05 | 2018-05-11 | 中国林业科学研究院林产化学工业研究所 | A kind of colorless terpene resin and its preparation process |
| CN108484804A (en) * | 2018-03-14 | 2018-09-04 | 吉安科茂树脂有限公司 | A kind of high solids content low softening point light color liquid terpene resin and the preparation method and application thereof |
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| CN102898564A (en) * | 2012-11-01 | 2013-01-30 | 张道飘 | Method for preparing terpene resin |
| CN102898564B (en) * | 2012-11-01 | 2015-07-22 | 张道飘 | Method for preparing terpene resin |
| CN103450395B (en) * | 2013-08-28 | 2016-01-06 | 梧州市嘉盈树胶有限公司 | The preparation method of terpine resin |
| CN103450395A (en) * | 2013-08-28 | 2013-12-18 | 梧州市嘉盈树胶有限公司 | Preparation method of terpene resin |
| CN103450376A (en) * | 2013-08-29 | 2013-12-18 | 江西麻山化工有限公司 | Distillation process for synthetic resin production process |
| CN103450376B (en) * | 2013-08-29 | 2016-01-20 | 江西麻山化工有限公司 | A kind of for the synthesis of the distil process in production of resins process |
| CN104211843B (en) * | 2014-08-14 | 2016-08-24 | 广西众昌树脂有限公司 | The preparation method of terpene resin |
| CN104211843A (en) * | 2014-08-14 | 2014-12-17 | 广西众昌树脂有限公司 | Preparation method of terpene resin |
| CN104877075A (en) * | 2015-05-19 | 2015-09-02 | 广西众昌树脂有限公司 | Method for producing terpene resin by taking turpentine as raw material |
| CN104910303A (en) * | 2015-05-27 | 2015-09-16 | 梧州市嘉盈树胶有限公司 | Method for preparing terpene resin by using dipentene as raw material |
| CN106519534A (en) * | 2016-12-05 | 2017-03-22 | 罗定市星光化工有限公司 | Production process of food-grade terpene resin |
| CN106519534B (en) * | 2016-12-05 | 2018-09-28 | 罗定市星光化工有限公司 | A kind of production technology of food-grade terpene resin |
| CN108017739A (en) * | 2017-12-05 | 2018-05-11 | 中国林业科学研究院林产化学工业研究所 | A kind of colorless terpene resin and its preparation process |
| CN108484804A (en) * | 2018-03-14 | 2018-09-04 | 吉安科茂树脂有限公司 | A kind of high solids content low softening point light color liquid terpene resin and the preparation method and application thereof |
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Application publication date: 20120815 |