CN1040992C - High-output non-acid-residue process for preparing poly-rosin - Google Patents
High-output non-acid-residue process for preparing poly-rosin Download PDFInfo
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- CN1040992C CN1040992C CN93114805A CN93114805A CN1040992C CN 1040992 C CN1040992 C CN 1040992C CN 93114805 A CN93114805 A CN 93114805A CN 93114805 A CN93114805 A CN 93114805A CN 1040992 C CN1040992 C CN 1040992C
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Abstract
The present invention discloses a method for preparing polymerized rosin, which adopts sulphuric acid-acetic acid as catalysts; raw material rosin is dissolved into toluene or dimethylbenzene xylene, and after the following steps: polymerization reaction, washing, distillation, etc., the yield of the polymerized rosin is 91 to 93%, and acid sludge can not be generated in the preparing process.
Description
The invention belongs to a kind of rosin secondary processing technology, specifically the preparation method of polymerized rosin.
Polymerized rosin is the Abietyl modified product of rosin secondary processing, owing to it has lighter color, softening temperature height, the non-crystallizable industries such as printing ink, coating, tackiness agent and synthetic resins that are widely used in.
Polymerized rosin normally is dissolved in the catalyzer of making polyreaction in gasoline or toluene, dimethylbenzene, the chloroform with sulfuric acid, zinc chloride or hydrogen fluoride to rosin, carry out cationic polymerization at a certain temperature, generate mainly to contain a kind of rosin reprocessing product of dimer rosiny.Be divided into 115 with different dimer contents or softening temperature
#With 140
#Two kinds of trades mark.
At present, preparing the method for polymerized rosin, is to select different catalyzer to divide, sulfuric acid process, zinc chloride process, sulfuric acid monochlor(in)ate zinc method, hydrochloric acid monochlor(in)ate zinc method etc. are arranged.
It is the method for Preparation of Catalyst polymerized rosin with hydrochloric acid-zinc chloride that Japanese Patent (the clear 45-35794 of Japan's special permission bulletin) has been introduced a kind of, and the step of this method is dissolving-acid isomer-thermal dehydration-zinc chloride polymerization-washing-distillation.Though this method can obtain the product of high yield.But this method operation steps is many, and dehydration is difficult to influence fully and directly next step polymerization process behind the isomery.
It is the method for Preparation of Catalyst polymerized rosin that sulfuric acid-zinc chloride process is adopted in the chemical plant, Guilin, though more original sulfuric acid process has bigger improvement, but dissolving, isomerization reaction, polyreaction adopt the condition control of three phases respectively, red-tape operati is difficult, owing to adopt the sulfuric acid isomery, the unavoidable sulfonation reaction that takes place produces emulsion in the reaction, cause difficulty to washing, influenced quality product.
Aforesaid method brings the oxidation side reaction in cationic polymerization, the waste residue that makes local rosin be oxidized into insoluble not fusant under the acid effect is precipitated out, and claims acid sludge again.Because these acid sludges do not have utility value, cause environmental pollution again.For this reason, many in recent years researchers have been created many methods, attempt to address this problem, select for use methylsulphonic acid and trimethylammonium sulfonic acid as making catalyzer with formic acid in catalyzer US 4536333 patents in US 4339377 patents, CN86101032 selects then that hydrogenchloride---zinc chloride is made catalyzer for use, and these improve the method for preparing polymerized rosin, and productive rate is on the low side, still have a small amount of acid sludge to produce, unsatisfactory.Especially use that hydrogenchloride---zinc chloride is made catalyzer, reaction control is difficult, and is when these catalyzer of recycling, more serious to the corrosion of equipment simultaneously.Bring the maintenance of equipment difficulty, investment and cost increase.Cause secondary pollution, be difficult to carry out suitability for industrialized production.
The objective of the invention is to exist acid sludge to pollute and the low problem of productive rate in the polymerized rosin production for solving, having proposed a kind of high yield does not have the method that acid sludge prepares polymerized rosin.
Main technique method of the present invention is:
1, with rosin is starting raw material;
2, above-mentioned raw materials is dissolved in toluene or the xylene solvent;
3, under the heating in water bath whipped state, drip sulfuric acid---acetic acid catalyst, carry out
Polyreaction.
4, the hot water wash reaction solution is to remove disacidify
5, above-mentioned product is distilled, reclaims solvent, obtain the finished product.
The present invention has avoided independent use sulfuric acid catalyst to cause local reaction violent owing to used sulfuric acid---acetate novel polymerization catalyst, so rosin can not be oxidized to insoluble infusible acid sludge, because acetate improves productive rate with vitriolic composite catalyzing effect.Sulfuric acid---acetic acid catalyst is compared with the polymerizing catalyst of other use, is easy to control and handles simply in reaction process, can not cause secondary pollution.
Concrete processing method of the present invention is: raw material rosin is dropped in the reactor, add solvent toluene or dimethylbenzene simultaneously, its weight ratio is a solvent: rosin=1: 1～2: 1, and 30～50 ℃ of stirred in water bath dissolvings.
Under agitation dripping its quantity of sulfuric acid-acetic acid catalyst is raw material rosin weight
10～20%, in half an hour, dropwise, continue to keep 30～50 ℃ of thermotonuses afterwards 4～6 hours, stop reaction, with 40～60 ℃ hot water wash reaction solutions 3～5 times, the water that is washed till lower floor is for neutrality (pH6～7), so that remove residual acid.With the product distillating recovering solvent, distillation temperature heat-up rate before 120 ℃ is controlled at per hour to heat up and is no more than 10 ℃ in still-process, is warming up to 260 ℃ and finishes distillation procedure, obtains the finished product.
Embodiment
The raw material medicine: one-level rosin, toluene or dimethylbenzene, sulfuric acid, acetate are dissolved in rosin in solvent toluene or the dimethylbenzene solvent: rosin (w/w)=2: 1～1: 1, sulfuric acid mixes (w/w=4: 1～6: 1) with acetate.
Operation: get in the four-hole bottle that rosin solution is incorporated with thermometer, agitator, dropping funnel, use heating in water bath, drip sulfuric acid-acetate mixed solution under agitation 30 minutes, continue reaction after 5 hours, stop reacting.Remove acid solution 3～5 times with 40～60 ℃ hot water wash, be washed till pH6～7, at distillating recovering solvent below 260 ℃.
Sample is pressed ZBB72008-89, and the method for stipulating in the polymerized rosin industry standard is measured.
Embodiment reaction conditions and measurement result see Table 1
Table 1 embodiment reaction conditions and measurement result
| The embodiment numbering | One | Two | Three |
| Rosin solution (gram) | 200 | 200 | 2000 |
| Catalyzer (gram) | 18.5 | 18.5 | 185 |
| Temperature of reaction (℃) | 30 | 50 | 40 |
| Yield: (%) | 93 | 91 | 93 |
| Softening temperature (℃) | 124 | 128 | 125 |
| Dimer content (%) | 18.7 | 25.1 | 18.7 |
| Color and luster Q | 7 | 8 | 7 |
| Acid number | 150 | 155 | 158 |
| Alcohol-insoluble substance (%) | Do not measure | Do not measure | Do not measure |
| The hot water solubles (%) | 0.07 | 0.10 | 0.12 |
| Outward appearance | Transparent | Transparent | Transparent |
In raw material rosin is 100%
Claims (8)
1, a kind of preparation method of polymerized rosin is characterized in that:
(1) with rosin is raw material;
(2) above-mentioned raw materials is dissolved in toluene or the xylene solvent;
(3) dripping sulfuric acid-acetic acid catalyst under the heating in water bath whipped state advances
The row polyreaction;
(4) use the hot water wash reaction solution;
(5) will go up product and distill, obtain the finished product.
2, preparation method according to claim 1 is characterized in that solvent toluene or dimethylbenzene and raw material rosin consumption are 1: 1～2: 1 by weight.
3, preparation method according to claim 1 is characterized in that rosin dissolved temperature in solvent is 30～50 ℃.
4, preparation method according to claim 1 is characterized in that sulfuric acid-acetic acid catalyst consumption is 10～20% of a raw material rosin weight.
5, according to claim 1 or 4 described preparation methods, it is characterized in that described Preparation of catalysts method is that sulfuric acid is mixed with acetate, the weight ratio of sulfuric acid and acetate is 4: 1～6: 1.
6, preparation method according to claim 1 is characterized in that finishing in 30 minutes the dropping of catalyzer, reacts 4～6 hours under 30～50 ℃ of temperature.
7, preparation method according to claim 1 is characterized in that being 6～7 with 40～60 ℃ hot water wash reaction solution 3～5 times until the pH of lower layer of water.
8, preparation method according to claim 1 is characterized in that in the still-process, and distillation temperature per hour heated up and is no more than 10 ℃ before 120 ℃, was warming up to 260 ℃ and stopped distillation procedure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93114805A CN1040992C (en) | 1993-11-17 | 1993-11-17 | High-output non-acid-residue process for preparing poly-rosin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93114805A CN1040992C (en) | 1993-11-17 | 1993-11-17 | High-output non-acid-residue process for preparing poly-rosin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1105378A CN1105378A (en) | 1995-07-19 |
| CN1040992C true CN1040992C (en) | 1998-12-02 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93114805A Expired - Fee Related CN1040992C (en) | 1993-11-17 | 1993-11-17 | High-output non-acid-residue process for preparing poly-rosin |
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| Country | Link |
|---|---|
| CN (1) | CN1040992C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100350007C (en) * | 2005-04-24 | 2007-11-21 | 青岛科技大学 | Process for preparing newtrex |
| CN1304508C (en) * | 2005-12-30 | 2007-03-14 | 北京科技大学 | Process for removing insoluble matter in solution of polycolophony methylbenzene |
| CN100358958C (en) * | 2006-03-09 | 2008-01-02 | 古远亮 | Production of rosin from natural pine gum |
| CN102344751B (en) * | 2011-06-30 | 2014-03-12 | 广西大学 | Method for simultaneously preparing terpene rosin resin and polymerized rosin from rosin as raw material |
| CN104212357B (en) * | 2014-08-14 | 2016-05-25 | 广西众昌树脂有限公司 | The preparation method of newtrex |
| CN104212356B (en) * | 2014-08-14 | 2016-05-25 | 广西众昌树脂有限公司 | The preparation method of newtrex |
| CN108727989A (en) * | 2018-06-27 | 2018-11-02 | 广西浙缘农业科技有限公司 | The synthetic method of newtrex |
| CN113897139A (en) * | 2021-11-08 | 2022-01-07 | 怀化市新谱乐器有限公司 | Micro-dust rosin for musical instruments and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065473A (en) * | 1991-11-18 | 1992-10-21 | 湖南省浏阳县林产品厂 | New technology for producing rosin |
-
1993
- 1993-11-17 CN CN93114805A patent/CN1040992C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065473A (en) * | 1991-11-18 | 1992-10-21 | 湖南省浏阳县林产品厂 | New technology for producing rosin |
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| Publication number | Publication date |
|---|---|
| CN1105378A (en) | 1995-07-19 |
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