CN1273542C - Producing method for high softening point polymer resin - Google Patents
Producing method for high softening point polymer resin Download PDFInfo
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- CN1273542C CN1273542C CN 200410027621 CN200410027621A CN1273542C CN 1273542 C CN1273542 C CN 1273542C CN 200410027621 CN200410027621 CN 200410027621 CN 200410027621 A CN200410027621 A CN 200410027621A CN 1273542 C CN1273542 C CN 1273542C
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Abstract
The present invention relates to a producing method for high softening point polymerized rosin, which comprises the steps comprising polymerization, washing, distillation, refining, film making, packing and the like. In the method, rosin is used as a raw material, gasoline is used as a solvent, strong sulphuric acid is dropped and added in cooling environment, cation polyreaction is carried out to obtain a dipolymer resinic acid fat liquid, and clarification and separation are carried out; solid carbonic acid ammonium is neutralized with a material liquid until a pH value is 6.5, the mixed material liquid is washed in hot water in a washing tower, the fat liquid is poured in a distilling tower to make the gasoline distilled off, polymerized rosin is separated out, and the mixed liquid of rosin / rosin oil is fractionated; the mixed liquid passes a fractional condenser to obtain fractionation rosin or 861 resin with a softening point of 68 DEG C to 78 DEG C; the separated polymerized rosin can be directly packed by an iron drum and can also enter a refining kettle, a proper quantity of resin acid monomers are added, heated and refined to obtain high softening point polymerized rosin. The method is complete in polyreaction, less in side reaction and high in a softening point of a product of the method, and the product does not contain zinc; the method can be used for food industry and food packing industry, a neutralization technology used in the method solves the problem of 'tower blocking'; clarification is carried out first, and the water washing effects are good; mass production proves that in the process of the method, the quality of a product is good, and the method is suitable for the mass industrialized production with high requirements on a softening point.
Description
Technical field
The present invention relates to a kind of production method of polymerized rosin, particularly a kind of production method that is mainly used in the high softening-point polymerized rosin of food and food packaging industry.
Background technology
Polymerized rosin is to be raw material with rosin, through cationic polymerization, generates a kind of transparent amorphous solid resin that mainly contains dimer resinous acid.It belongs to rosin secondary processing modified product, than raw material rosin, it has characteristics such as lighter color, softening temperature height, non-crystallizable, not oxidation, in fields such as printing-ink, coating, glue paste, solubility promoters, as tackiness agent and additive composition and be used widely.The softening temperature of polymerized rosin is the important parameter that influences its product performance, depends on the wherein height of dimer content, just the size of its polymerization degree.Preparation method's system of existing polymerized rosin, there is several different methods in different according to catalyst system and solvent, and the postprocessing working procedures after the polymerization also has nothing in common with each other.The industry standard ZBB72008-89 of the People's Republic of China (PRC) " polymerized rosin " is with the difference of product by dimerization resinous acid content.Be the difference of softening temperature, be divided into 115 and 140 two kind of trade mark, wherein the softening temperature of 115# is 110 ℃～120 ℃ scopes, and the softening temperature of 140# is 135 ℃～145 ℃ scopes.Relevant polymerized rosin preparation method's report all relates to the product of these two kinds of trades mark.As for the 145# product, particularly be applicable to the polymerized rosin and the production method thereof of the high softening-point (softening temperature does not contain zinc at 141 ℃～150 ℃) of food and food packaging industry, still be not reported.
No. 861 01032, Chinese patent ZL " hydrogenchloride monochlor(in)ate zinc is produced the method for polymerized rosin " (notification number CN1013582B), the method of being announced comprises reaction (dissolving, isomerization reaction, polyreaction), washing, distillation three process such as (interrupter methodes), warm eventually in distillation process control distillation, can obtain certain product among the trade mark 100-140 respectively.Because in dissolving, isomerization and the polymerization of reaction process, adopt the condition control of three phases, reaction control is difficult; Particularly owing to adopt zinc chloride to make catalyzer, the finished product contain zinc and can not be used for food and food packaging industry.931 No. 14805.7 " a kind of preparation method of polymerized rosin " (notification number CN 1040992C) of ZL have announced employing sulfuric acid-acetate and have made catalyzer, make solvent with toluene or dimethylbenzene, through the preparation technology of steps such as polyreaction, washing, distillation.It is said that this invention uses sulfuric acid-acetate to make catalyzer, the local reaction of having avoided independent use sulfuric acid catalyst to be caused is violent, the unlikely acid sludge that is oxidized to of rosin, and the result of composite catalyzing improves productive rate, to 91%～93%.Obviously, use aromatic solvent, can make production environment abominable, cause the degree of depth to pollute; Though its productive rate is higher, be that dimer content is lower thereupon, only be 18.7%; Main is this patent document is disclosed to be the preparation method of laboratory lab scale, solvent: the rosin solution amount of rosin=2: 1～1: 1 is 200 grams, a highest example 2000 grams.Obviously, its technology is not suitable for industrialized production. must cause the defective on the quality product.
Summary of the invention
The objective of the invention is to avoid the deficiencies in the prior art part, and provide a kind of its product to be mainly used in food and food packaging industry, softening temperature is higher, quality better polymerization rosiny production method.
Purpose of the present invention can reach by following measure:
A kind of production method of high softening-point polymerized rosin comprises polyreaction operation, washing reaction liquid operation and distillation process, and this production method also comprises refining step, wherein
1. polyreaction operation: with gasoline is solvent, 95% vitriol oil is a catalyzer, raw material rosin dissolves under 60 ℃～65 ℃ temperature through waiting petrol, enter reactor, under the refrigerative environment, drip 95% vitriol oil, 95% vitriol oil amount that adds is 10%～30% of a rosin weight, and reaction is 3 hours～5 hours under 40 ℃～70 ℃ temperature; Particularly, for producing 95 polymerized rosines, the dripping quantity of 95% vitriol oil is 10%, 3 hours reaction times; For producing 145 polymerized rosines, 95% vitriol oil amount is 30%, reacts 5 hours.
2. washing reaction liquid operation: the reaction solution after the polymerization, clarify, separate through clarifying tank, move on in the neutralization pot and neutralize with alkali, particularly use the solid carbonic acid ammonium to neutralize, be neutralized to material liquid PH value to 6.5, be transported to again in the washing tower,, obtain the polymerized rosin fat liquid of cleaning with this polymerized rosin fat liquid of 55 ℃～60 ℃ hot washes;
3. distillation process: through the polymerized rosin fat liquid of washing, deliver in the distillation tower and distill, reclaim gasoline, the control distillation temperature is at 200 ℃～300 ℃, isolates to contain softening temperature at 90 ℃～100 ℃ thick 95 polymerized rosines; Perhaps, isolate and contain softening temperature at 141 ℃～150 ℃ thick 145 polymerized rosines; In addition, the fractionation rosin/rosinol that comes out from distillation tower separates through partial condenser, and control partial condenser temperature is 250 ℃～270 ℃, isolates rosinol wherein from the top, obtains fractionation rosin or softening temperature at the bottom of the tower at 68 ℃～78 ℃ 861 resins.
4. refining step: the polymerized rosin from above-mentioned distillation tower obtains, enter refining kettle, look the height of product softening temperature, add an amount of resinous acid monomer, addition is 0%～20% of a polymerized rosin amount, at 250 ℃～270 ℃, heats 2 hours～5 hours; Promptly be thick 95 polymerized rosines that contain 90 ℃～100 ℃ of softening temperatures with described, add the resinous acid monomer, through heating refining 95 polymerized rosines that obtain; With described thick 145 polymerized rosines that contain 141 ℃～150 ℃ of softening temperatures, add the resinous acid monomer, heating is refining together, obtains 145 polymerized rosines.
The high softening-point polymerized rosin can barreled; Also can carry out the film-making packing of finished product, during film-making, polymerized rosin fat liquid is delivered to the packing groove, be processed into the thick thin slice of 1.6mm～2mm through pelleter again, use paper bag packing, particularly, be more suitable for using paper bag packing being used for the polymerized rosin of food and food packaging industry.
Method of the present invention has the following advantages:
1. though the still single catalyst that adopts, but owing to adopt cooling to drip the technology of 95% vitriol oil, temperature of reaction and rate of addition are all controlled better, greatly reduce rosin and be oxidized to acid sludge, and side reaction such as sulfonation, reaction is carried out more fully, the dimer content height, thereby, obtain the polymerized rosin of high softening-point with simple production technique.
2. because catalyst system is single, and the by product of introducing is few, does not particularly contain zinc, its product is applicable to food and food packaging industry.
3. this production method is through the checking of the long-time running of industrialized production, and quality product is good, and its softening temperature surpasses existing national sector standard, develops new trade mark polymerized rosin product, lays the foundation for working out new advanced company standard.
4. adopt solid carbonic acid ammonium neutralisation, solved " stifled tower " problem that existing technology often occurs.
5. replace aromatic hydrocarbon solvent with gasoline, alleviate the environmental pollution degree; Solvent is through repeatedly reclaiming, and the rate of recovery is higher.
6. adopt clarifying washing process, both alleviated the burden of hot water washing, promote again and clean effect.
Below in conjunction with drawings and Examples the inventive method is done further narration.
Description of drawings:
Fig. 1 is the process flow diagram of production method of the present invention, among the figure, the 1st, the fusion pot, the rosin that the 1-1 representative has been pulverized, 1-2 represents 200# gasoline, the 2nd, reactor, 2-1 is the sulphur acid meter measuring tank, 2-11 represents 95% vitriol oil, and 22 represent polymerized rosin reaction solution, the 3rd, clarifying tank, 31 represent polymerized rosin fat liquid, the sour water of 32 representative dischargings, acid sludge, the 4th, the neutralization pot, 41 represent the solid carbonic acid ammonium, water is gone up in 42 representatives, the waste water of 43 representative dischargings, the 5th, washing tower, 51 represent hot water, 52 represent waste water, the 6th, polymerized rosin fat liquid header tank, the 7th, distillation tower, 71 represent superheated vapour, 72 represent polymerized rosin, 73 represent fractionation rosin/rosinol mixed solution, and 74 representatives are water down, and the 8th, condenser, the gasoline that 81 representatives are reclaimed, the 9th, pail pack, 91 represent barreled polymerized rosin, the 10th, refining kettle, the resinous acid monomer that 101 representatives are added, the refining polymerized rosin of 102 representatives, 103 representatives are water down, and the 11st, pail pack, 111 represent barreled 95 polymerized rosines or 145 polymerized rosines, the 12nd, the packing groove, 121 represent high softening-point polymerized rosin, the 13rd, pelleter, 131 represent 95 polymerized rosines or 145 polymerized rosin thin slices, the 14th, partial condenser, 141 represent rosinol, and 142 represent fractionation rosin or 861 resins.
Embodiment
As shown in drawings, in production equipment as schematically shown in Figure 1, implement production method of the present invention, its main points, processing condition and product performance index are as follows.
1. the main points of production method of the present invention:
(1) with gum resin is raw material;
(2) the polyreaction solvent for use is No. 200 gasoline;
(3) under jacket reactor water-bath cooling, drip 95% vitriol oil and carry out polyreaction;
(4) use in the solid carbonic acid ammonium and the polymerized rosin reaction solution;
(5) use hot wash through clarifying polymerized rosin neutralizer;
(6) washed polymerized rosin fat liquid is distilled, isolate thick 95 polymerized rosines that contain 90 ℃～100 ℃ of softening temperatures; Perhaps isolate thick 145 polymerized rosines that contain 141 ℃～150 ℃ of softening temperatures;
(7), obtain 95 polymerized rosines or 145 polymerized rosines at the softening temperature of refining kettle inner control product;
(8) control finished product thickness at 1.6mm～2.0mm by pelleter.
(9) the product softening temperature is controlled to be: 95 polymerized rosines are at 90 ℃～100 ℃, and 145 polymerized rosines are at 141 ℃～150 ℃, and 861 resins are at 68 ℃～78 ℃.
(10) product can be applicable to food or food packaging industry.
(11) adopt paper bag packing 95 polymerized rosines and 145 polymerized rosines first.
2. the processing condition of this production method:
(1) dissolving
The ratio of gum resin and gasoline and dissolution conditions:
Gum resin: gasoline=1: 1
Temperature: 60 ℃～65 ℃
(2) polyreaction:
Drip the ratio of 95% vitriol oil, be 10%～30% of rosin weight, reaction is 3 hours～5 hours under 40 ℃～70 ℃ temperature, particularly
To 95 polymerized rosines, the dripping quantity of 95% vitriol oil is 10% of a rosin weight, 3 hours reaction times;
To 145 polymerized rosines, the dripping quantity of 95% vitriol oil is 30% of a rosin weight, 5 o'clock reaction times;
(3) clarification condition
Settling time: 6 hours～8 hours
(4) neutrality condition
Adopt the neutralization of solid carbonic acid ammonium, the control material liquid PH value is 6.5
(5) wash conditions:
Use hot wash, 55 ℃～60 ℃ of water temperatures.
(6) distillation condition
The control distillation temperature when separation contains thick 95 polymerized rosines of 90 ℃～100 ℃ of softening temperatures, is controlled at 220 ℃～250 ℃ at 200 ℃～300 ℃; When separation contains thick 145 polymerized rosines of 141 ℃～150 ℃ of softening temperatures, be controlled at 270 ℃～285 ℃.
(7) partial condenser condition:
Product: 861 resins (68 ℃～78 ℃ of softening temperatures) or fractionation rosin; And condensation goes out rosinol control partial condenser temperature: 250 ℃～270 ℃
(8) refining kettle condition:
The height of looking the product softening temperature adds the resinous acid monomer, adding proportion in right amount:
Monomer: thick polymerized rosin=0: 1～0.2: 1
Temperature: 250 ℃～270 ℃
Time: 2 hours～5 hours
Wherein, when making with extra care 95 polymerized rosines, use thick 95 polymerized rosines that contain 90 ℃～100 ℃ of softening temperatures; When making with extra care 145 polymerized rosines, use thick 145 polymerized rosines that contain 141 ℃～150 ℃ of softening temperatures;
(9) film-making condition:
Control finished product thickness 1.6mm～2.0mm.
3. the physical and chemical index of product:
| Project | Index | |||
| 95 polymerized rosines | 145 polymerized rosines | 861 resins | ||
| Outward appearance | Transparent | Transparent | Transparent | |
| Color | China's rosin color grading standard is shallower than or equals | Three grades | Three grades | Superfine |
| U.S.'s rosin color grading standard is shallower than or equals | The N level | The N level | The X level | |
| Ghana's look number is shallower than or equals | 9 | 9 | 6 | |
| Softening temperature (ring and ball method), ℃ | 90～100 | 141～150 | 68～78 | |
| Acid value, mgKOH/g 〉= | 155 | 140 | 130 | |
| The Virahol solubility test | - | Qualified | - | |
Claims (10)
1. the production method of a high softening-point polymerized rosin comprises polyreaction operation, washing reaction liquid operation and distillation process, it is characterized in that, this production method also comprises refining step, and the feature of each operation is as follows:
(1) polyreaction operation: with gasoline is solvent, 95% vitriol oil is a catalyzer, raw material rosin is through waiting petrol dissolving, enter reactor, under the refrigerative environment, drip 95% vitriol oil and make catalyzer, 95% vitriol oil amount that adds is 10%～30% of a rosin weight, and reaction is 3 hours～5 hours under 40 ℃～70 ℃ temperature;
(2) washing reaction liquid operation: the reaction solution of polymerization gained, clarify, separate through clarifying tank, move on in the neutralization pot with the alkali neutralization, be neutralized to material liquid PH value to 6.5, be transported to again in the washing tower, with this polymerized rosin fat liquid of hot wash;
(3) distillation process: through the polymerized rosin fat liquid of washing, deliver in the distillation tower and distill, reclaim gasoline; The control distillation temperature is isolated and is contained softening temperature at 90 ℃～100 ℃ thick 95 polymerized rosines at 200 ℃～300 ℃; Perhaps, isolate and contain softening temperature at 141 ℃～150 ℃ thick 145 polymerized rosines; In addition, the fractionation rosin/rosinol mixed solution from distillation tower comes out separates through partial condenser, and acquisition fractionation rosin or softening temperature are 68 ℃～78 ℃ 861 resins;
(4) refining step: the thick polymerized rosin from distillation tower obtains, enter refining kettle, add the resinous acid monomer that is equivalent to polymerized rosin amount 0%～20%, 250 ℃～270 ℃ heating 2 hours～5 hours down; Promptly be thick 95 polymerized rosines that contain 90 ℃～100 ℃ of softening temperatures with described, add the resinous acid monomer, through heating refining 95 polymerized rosines that obtain; With described thick 145 polymerized rosines that contain 141 ℃～150 ℃ of softening temperatures, add the resinous acid monomer, heating is refining together, obtains 145 polymerized rosines.
2. the production method of high softening-point polymerized rosin according to claim 1, it is characterized in that, this method also comprises the film-making packaging process of finished product: the purified polymerized rosin is delivered to the packing groove, is processed into the thin slice that thickness is 1.6mm～2.0mm through pelleter again, uses paper bag packing.
3. the production method of high softening-point polymerized rosin according to claim 1 and 2 is characterized in that, in described polyreaction, the dripping quantity and the reaction times of catalyzer 95% vitriol oil respectively for 95 polymerized rosines, are 10% and 3 hour; For 145 polymerized rosines, it is 30% and 5 hour.
4. the production method of high softening-point polymerized rosin according to claim 1 and 2 is characterized in that, the used alkali of described neutralization reaction liquid is the solid carbonic acid ammonium.
5. the production method of high softening-point polymerized rosin according to claim 3 is characterized in that, the used alkali of described neutralization reaction liquid is the solid carbonic acid ammonium.
6. the production method of high softening-point polymerized rosin according to claim 1 and 2 is characterized in that, the scope of described control distillation temperature when producing 95 polymerized rosines of 90 ℃～100 ℃ of softening temperatures, is controlled at 220 ℃～250 ℃; When producing 145 polymerized rosines of 141 ℃～150 ℃ of softening temperatures, be controlled at 270 ℃～285 ℃.
7. the production method of high softening-point polymerized rosin according to claim 3 is characterized in that, the scope of described control distillation temperature when producing 95 polymerized rosines of 90 ℃～100 ℃ of softening temperatures, is controlled at 220 ℃～250 ℃; When producing 145 polymerized rosines of 141 ℃～150 ℃ of softening temperatures, be controlled at 270 ℃～285 ℃.
8. the production method of high softening-point polymerized rosin according to claim 5 is characterized in that, the scope of described control distillation temperature when producing 95 polymerized rosines of 90 ℃～100 ℃ of softening temperatures, is controlled at 220 ℃～250 ℃; When producing 145 polymerized rosines of 141 ℃～150 ℃ of softening temperatures, be controlled at 270 ℃～285 ℃.
9. the production method of high softening-point polymerized rosin according to claim 1 and 2 is characterized in that, the control condition of described partial condenser, and controlled temperature is 250 ℃～270 ℃.
10. the production method of high softening-point polymerized rosin according to claim 8 is characterized in that, the control condition of described partial condenser, and controlled temperature is 250 ℃～270 ℃.
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| CN 200410027621 CN1273542C (en) | 2004-06-15 | 2004-06-15 | Producing method for high softening point polymer resin |
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| CN 200410027621 CN1273542C (en) | 2004-06-15 | 2004-06-15 | Producing method for high softening point polymer resin |
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| CN1273542C true CN1273542C (en) | 2006-09-06 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| JP2008266597A (en) * | 2007-03-22 | 2008-11-06 | Arakawa Chem Ind Co Ltd | Polymeric rosin, hydrogenated polymeric rosin and production method of these rosins, as well as flux and solder paste using these rosins |
| 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 |
| CN111393996B (en) * | 2020-04-21 | 2022-02-15 | 广东科茂林产化工股份有限公司 | Polymerized rosin mixed ester and preparation method and application thereof |
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