CN104829820B - The preparation method of a kind of high molecular polymerization catalyst and application - Google Patents
The preparation method of a kind of high molecular polymerization catalyst and application Download PDFInfo
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- CN104829820B CN104829820B CN201510237159.XA CN201510237159A CN104829820B CN 104829820 B CN104829820 B CN 104829820B CN 201510237159 A CN201510237159 A CN 201510237159A CN 104829820 B CN104829820 B CN 104829820B
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Abstract
The invention discloses preparation method and the application process of this high molecular polymerization catalyst of a kind of high molecular polymerization catalyst.Described preparation method sequentially includes the following steps: and is added by manganese acetate in Isosorbide-5-Nitrae butanediol, and then mix and blend is added thereto to isopropyl titanate, continuous stirring 0.5～1h at 220～240 DEG C, adds stannous octoate, continuous stirring 1～2h, obtains catalyst.The method that the present invention prepares high molecular polymerization catalyst is simple, it is easy to operation, and reaction condition is gentle, the most lasting industrialized production.
Description
Technical field
The invention belongs to Polymer Synthesizing field, relate to the preparation method of a kind of high molecular polymerization catalyst, further relate to this catalyst
Application.
Background technology
High molecular polymer refers to that, simple construction unit identical by many repeats the high molecular being formed by connecting by covalent bond
(generally up to 10～106) compound.The polymer being polymerized by a kind of monomer is referred to as homopolymer, as above polrvinyl chloride,
Polyethylene etc..Copolymer then it is referred to as, such as vinyl chloride acetate ethylene copolymer by the polymer of two or more monomer copolymerizations
Deng.Polymer catalyst is a kind of macromolecule to chemical reaction with catalytic action.Enzyme in organism is exactly a kind of high alive
Property, high selective natural polymer catalyst, but owing to being water miscible, therefore be restricted in commercial Application, because of and
Develop water-fast immobilized enzyme-a kind of semisynthetic polymer catalyst.The synthesis macromolecule catalysis of exploitation application at present
Agent mainly has ion exchange resin type catalyst and polymeric reduction two class.It is many with organic or inorganic macromolecule as skeleton,
Skeleton is connected with the various functional group with catalytic action.This kind of catalyst not only has the highest activity and selectivity, and
And more stable, separate, reclaim conveniently, can reuse, have also has the special functions such as optical activity.The most
It is applied in various organic reaction, organic synthesis and some macromolecular synthetic reaction.
Commercial production is applied and is studied more polymeric reduction and is mainly antimony, germanium, three serial chemical combination of titanium at present
Thing.Use the catalysis activity height of antimony-based catalyst, low price but there is toxicity, easily cause pollution in process of production,
Add post processing expense；The polyester slice white of germanium series polyester catalyst synthesis and highly transparent, form and aspect are preferable, but its catalysis
Specific activity antimony system is low, gained polyester ehter bond is more, fusing point is relatively low, additionally due to the germanium resource in nature is rare, stannum system is catalyzed
Agent is expensive, which also limits its extensive application in production of polyester；Therefore Titanium series catalyst is due to its higher catalysis work
Property and Safety and Environmental Protection become a kind polyester catalyst of current most study.
The most conventional Titanium series catalyst is butyl titanate or tetraisopropyl titanate, although but its activity is higher unstable, easy
Hydrolysis, the catalyst employed in such as patent CN1861660A be tetrabutyl titanate, isopropyl titanate, antimony oxide and
Germanic acid N-butyl.The patent application of Publication No. CN101935513B discloses the preparation of a kind of polyesteramide hot melt adhesive with low melting point
Method, the preparation of this PUR mainly comprises the steps: that (1) p-phthalic acid and propylene glycol and diethylene glycol are at butyl titanate
Under catalyst action, carry out esterification；(2) by M-phthalic acid, aliphatic dicarboxylic acid, decamethylene diamine and caprolactam add
The product of step (1), carries out being esterified and amidation process；(3) in above-mentioned reaction system, polycondensation stabilizer 2, the 6-tert-butyl group are added
-4-methylphenol, copolycondensation of then reducing pressure, it is thus achieved that copolymer.But, in actual production, single titanate ester is catalyzed
Agent often can't fully meet requirement, needs to compound with some other compound, forms composite catalyst.How to obtain outstanding
Catalyst compounded be this area research focus.
Summary of the invention
Goal of the invention: the invention provides the preparation method of a kind of high molecular polymerization catalyst and answering of this high molecular polymerization catalyst
Use method.
Technical scheme: the preparation method of high molecular polymerization catalyst of the present invention, sequentially includes the following steps:
Manganese acetate is added in BDO, mix and blend, be then added thereto to isopropyl titanate, at 220～240 DEG C
Lower continuous stirring 0.5～1h, adds stannous octoate, continuous stirring 1～2h, obtains catalyst precursor.Body before catalyst
Body adds calcium aluminate, obtains catalyst.
Described manganese acetate is 0.1～0.4:10 with the mol ratio of BDO；
Described isopropyl titanate is 1～1.4:10 with the mol ratio of BDO；
The addition of described stannous octoate is the 10～20% of the quality of BDO.
The addition of described calcium aluminate is the 3～5% of the quality of BDO.
The application of the catalyst of above-mentioned gained: mixed with BDO by succinic acid, carries out esterification anti-at 200～250 DEG C
Should, after esterification terminates, adding above-mentioned catalyst, start polycondensation reaction, the temperature of polycondensation reaction is
220～270 DEG C, pressure 30～40Pa, after reacting 1～3 hour, obtain polymer.
The quality of the addition of described catalyst is the 2～3% of 1,4 butanediols.
Beneficial effect: the present invention prepares that the method for high molecular polymerization catalyst is simple, easily operated, reaction condition is gentle, passes through
The addition of regulation stannous octoate, can prepare the catalyst of different performance.High molecular polymerization catalyst stabilization prepared by the present invention
Property is good, production cost is low, the most lasting industrialized production.
Detailed description of the invention:
Embodiment 1
In flask, add the BDO of 0.55mol, incorporate 0.015mol manganese acetate wherein, be then added thereto to
0.067mol isopropyl titanate, continuous stirring, react 1 hour at 230 DEG C, add stannous octoate 5g, continuous stirring 2
After hour, add addition calcium aluminate 3g, continue stirring 2 hours, obtain catalyst 1.
Embodiment 2
In flask, add the BDO of 0.55mol, incorporate 0.015mol manganese acetate wherein, be then added thereto to
0.067mol isopropyl titanate, continuous stirring, react 1 hour at 220 times, add stannous octoate 5g, continuous stirring 2
After hour, add addition calcium aluminate 4g, continue stirring 2 hours, obtain catalyst 2.
Embodiment 3
In flask, add the BDO of 0.55mol, incorporate 0.015mol manganese acetate wherein, be then added thereto to
0.067mol isopropyl titanate, continuous stirring, react 1 hour at 220 times, add stannous octoate 6g, continuous stirring 2
After hour, add calcium aluminate 5g, continue stirring 2 hours, obtain catalyst 3.
Embodiment 4
Being mixed with 54.07g BDO by 59.05g succinic acid, carry out esterification at 230 DEG C, esterification terminates
After, adding the catalyst 1 obtained in embodiment 1, the addition of catalyst 1 is the 2% of Isosorbide-5-Nitrae butanediol quality, starts contracting
Poly-reaction, the temperature of polycondensation reaction is 220 DEG C, and reaction pressure is 30Pa, after reacting 1 hour, obtains polymer 1.
Embodiment 5
Being mixed with 54.07g BDO by 59.05g succinic acid, carry out esterification at 230 DEG C, esterification terminates
After, adding the catalyst 2 obtained in embodiment 2, the matter of the addition of catalyst 2 is the 2% of Isosorbide-5-Nitrae butanediol quality, starts
Polycondensation reaction, the temperature of polycondensation reaction is 250 DEG C, and reaction pressure is 35Pa, after reacting 2 hours, obtains polymer 2.
Embodiment 6
Being mixed with 54.07g BDO by 59.05g succinic acid, carry out esterification at 230 DEG C, esterification terminates
After, adding the catalyst 3 obtained in embodiment 3, the quality of the addition of catalyst 3 is the 2% of Isosorbide-5-Nitrae butanediol, starts contracting
Poly-reaction, the temperature of polycondensation reaction is 250 DEG C, and reaction pressure is 35Pa, after reacting 2 hours, obtains polymer 3.
The result of above-mentioned test is as shown in the table:
Claims (7)
1. the preparation method of a high molecular polymerization catalyst, it is characterized in that, sequentially include the following steps: and manganese acetate is added 1, in 4-butanediol, mix and blend, then it is added thereto to isopropyl titanate, continuous stirring 0.5～1h at 220～240 DEG C, add stannous octoate, continuous stirring 1～2h, obtain catalyst precursor；In catalyst precursor, add calcium aluminate, obtain catalyst.
2. the preparation method of high molecular polymerization catalyst as claimed in claim 1, it is characterised in that described manganese acetate is 0.1～0.4:10 with the mol ratio of BDO.
3. the preparation method of high molecular polymerization catalyst as claimed in claim 1, it is characterised in that described isopropyl titanate is 1～1.4:10 with the mol ratio of BDO.
4. the preparation method of high molecular polymerization catalyst as claimed in claim 1, it is characterised in that the addition of described stannous octoate is the 10～20% of the quality of BDO.
5. the preparation method of high molecular polymerization catalyst as claimed in claim 1, it is characterised in that the addition of described calcium aluminate is the 3～5% of the quality of BDO.
6. the application of a high molecular polymerization catalyst, it is characterized in that succinic acid and 1,4-butanediol mixes, at 200～250 DEG C, carry out esterification, after esterification terminates, add the catalyst that method as claimed in claim 1 prepares, start polycondensation reaction, the temperature of polycondensation reaction is 220～270 DEG C, pressure 30～40Pa, after reacting 1～3 hour, obtains polymer.
Apply the most as claimed in claim 6, it is characterised in that the amount of the addition of catalyst is the 2～3% of BDO quality.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103214659A (en) * | 2013-03-25 | 2013-07-24 | 山东汇盈新材料科技有限公司 | High molecular weight bio-based poly(butylene succinate) synthesis method |
| CN104558549A (en) * | 2013-10-11 | 2015-04-29 | 中国石油化工股份有限公司 | A preparing method of aliphatic/aromatic copolyester |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103214659A (en) * | 2013-03-25 | 2013-07-24 | 山东汇盈新材料科技有限公司 | High molecular weight bio-based poly(butylene succinate) synthesis method |
| CN104558549A (en) * | 2013-10-11 | 2015-04-29 | 中国石油化工股份有限公司 | A preparing method of aliphatic/aromatic copolyester |
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Address after: 215138 No. 1 Zhangtangbangxiang, Yangchenghu Town, Xiangcheng District, Suzhou City, Jiangsu Province Patentee after: Suzhou Xiangyuan New Materials Co., Ltd. Address before: Suzhou City, Xiangcheng District province 215138 Jiangsu Yangchenghu town (Hunan City) ten Village Patentee before: Suzhou Xiangyuan Speical Fine Chemical Co., Ltd. |