CN102964589A - Preparation method of branched nylon resin - Google Patents
Preparation method of branched nylon resin Download PDFInfo
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- CN102964589A CN102964589A CN2012105246973A CN201210524697A CN102964589A CN 102964589 A CN102964589 A CN 102964589A CN 2012105246973 A CN2012105246973 A CN 2012105246973A CN 201210524697 A CN201210524697 A CN 201210524697A CN 102964589 A CN102964589 A CN 102964589A
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Abstract
The invention provides a preparation method of branched nylon resin. The preparation method is characterized in that one of phosphoric acid, organic phosphate and amino acid or a mixture of phosphoric acid, organic phosphate and amino acid is taken as a catalyst for ring opening of caprolactam, so that ring opening polymerization speed of the caprolactam is effectively increased. Compared with the hydrolyzed ring opening polymerization of caprolactam, the preparation method provided by the invention has the characteristics of high reaction speed, low polymerization temperature, short production period and the like.
Description
Technical field
The present invention relates to the polymkeric substance preparation field, relate in particular to a kind of preparation method of branched chain nylon resin.
Background technology
Tynex is commonly called as nylon (Nylon), and English name Polyamide(is called for short PA), density 1.15g/cm3; , be contain on the molecular backbone chain recurring amide radical group-[NHCO]-the thermoplastic resin general name.Comprise aliphatics PA, fat-aromatic series PA and aromatic series PA.Wherein, aliphatics PA is wide in variety, and output is large, is widely used, and its name is decided by the concrete carbonatoms of synthon.Famous American chemist Tomas Carothers and the invention of his scientific research group.Nylon is a kind of saying of tynex (polyamide fibre), can be made into long fibre or short fiber.
In recent years, along with the equipment unit of the industries such as automobile, electronics and the machinery trend to lightweight and miniaturization development, but the high nylon material that flows rapid shaping of exploitation becomes the focus of new product development.A kind of synthesis preparation method of branched chain nylon resin in being 201110233490.6 Chinese patent, has been described application number.This preparation method introduces a branch chain structure in the nylon molecule, so that side chain nylon is under the prerequisite that its mechanical properties remains unchanged, the more linear nylon of fluidity of molten and shock strength increases exponentially, and efficiently solves the mobile bad problem of linear nylon.This patent is adopted and is used water as initiator, and polymerization time is longer, and temperature of reaction is high, and polymerization pressure is high, and energy consumption is large, thereby makes the synthetic cost of side chain nylon high, has limited suitability for industrialized production and the application of side chain nylon.
Summary of the invention
The invention reside in and provide that a kind of speed of response is fast, polymerization temperature is low, the preparation method of with short production cycle, branched chain nylon resin that the material consumption energy consumption is low.
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of branched chain nylon resin, comprising:
Caprolactam monomer, catalyzer and properties-correcting agent are mixed to get mixture and obtain side chain nylon after carrying out ring-opening reaction under 200-260 ℃.
Preferably, described catalyzer is phosphoric acid, phosphoric acid ester, phosphorous acid ester and amino acid whose one or more mixture.
Described cladodification properties-correcting agent is any one in Amino Terminated polyether(ATPE) compound, end carboxyl polyether compound, polyethyleneimine: amine compound and the Amino Terminated polyether(ATPE)/polymine mixing cpd.
Preferably, described phosphoric acid ester
General formula is: R
3PO
4,
Wherein R is hydrogen, and the carbon atom number is the alkyl of 1-18 or the phenyl of I formula institute formula
R
1It is 1 ~ 10 alkyl for hydrogen or carbon atom number.
Preferably, described amino acid has structure shown in the formula II
R wherein
2It is 6 ~ 12 alkyl for the carbon atom number.
Preferably, described catalyst loading is 0.1 ~ 5% of lactam monomers molar content.
Preferably, described cladodification agent addition is 1.0 ~ 5% of lactam monomers molar content.
Preferably, temperature of reaction is 200-260 ℃, and reaction pressure is normal pressure, and the reaction times is 8-10 hour.
The invention provides a kind of preparation method of branched chain nylon resin, may further comprise the steps: a) lactam monomers, catalyzer and properties-correcting agent are mixed to get the first mixture; Described catalyzer is any one in phosphoric acid, phosphoric acid ester, phosphorous acid ester, the amino acid; B) described the first mixture is warming up to 200 ~ 260 ℃, lactam monomers carries out obtaining the second mixture after the ring-opening reaction; C) described the second mixture is carried out the condensation polymerization reaction, obtain branched chain nylon resin.The present invention reduces ring-opening reaction activation energy, accelerates ring-opening reaction speed by adopting novel composite catalyst, can rapidly and efficiently prepare the good branched chain nylon resin of high workability and toughness.Compare with existing side chain technique for synthesizing nylon technology, advantage of the present invention is that polymerization temperature is low, and with short production cycle, process costs is low, and production efficiency is high, and material consumption, energy consumption are low, the characteristics that polymerization pressure is little.
Embodiment
The invention provides the method that a kind of catalysis method prepares branch chain nylon 6, its key is to adopt the catalyzer of oneself the interior acid amide ring-opening reaction of mixture conduct in phosphoric acid ester, amino acids or this two class.
The invention provides a kind of preparation method of side chain nylon, may further comprise the steps:
Caprolactam monomer, catalyzer and properties-correcting agent are mixed to get mixture and obtain side chain nylon after carrying out ring-opening reaction under 200-260 ℃.
Be specially:
A) lactam monomers, catalyzer and properties-correcting agent are mixed to get mixture; Described catalyzer is any one in phosphoric acid, phosphoric acid ester, phosphorous acid ester and the amino acid;
B) described mixture is warming up to 200 ~ 260 ℃, lactam monomers carries out obtaining the hexanolactam oligomer after the ring-opening reaction;
C) described hexanolactam oligomer is carried out the condensation polymerization reaction, obtain branched chain nylon resin.
Because the present invention's preparation is side chain nylon, so the monomer that uses and catalyzer need special selection, especially catalyzer, can effectively reduce polymerization temperature, shortens polymerization time, is key point of the present invention so use suitable catalyzer.According to the present invention, described catalyzer is any one in phosphoric acid, phosphoric acid ester, phosphorous acid ester, the amino acid; Be preferably the aqueous solution of phosphoric acid ester, phosphorous acid ester or phosphoric acid.The described phosphoric acid ester general formula of wherein said phosphoric acid ester is: R
3PO
4, R is that hydrogen, carbon atom number are 1 ~ 18 alkyl or the phenyl shown in the formula I:
R
1It is 1 ~ 10 alkyl for hydrogen or carbon atom number.
According to the present invention, described amino acid has structure shown in the formula II
R wherein
2It is 6 ~ 12 alkyl for the carbon atom number.
According to the present invention, described properties-correcting agent is by connect modified group at described polymeric amide molecular chain in polymerization process, thereby realize the functionalized of polymeric amide molecule, because the monomer that the present invention uses is caprolactam monomer, properties-correcting agent is preferably one or more in Amino Terminated polyether(ATPE) compound, end carboxyl polyether compound, polyethyleneimine: amine compound and the Amino Terminated polyether(ATPE)/polyethyleneimine: amine mixt
According to the present invention, described catalyzer accounts for 0.5 ~ 5% of lactam monomers molar content, more preferably 0.5-1.0%.Modifier compound accounts for 1.0% ~ 10% of lactam monomers molar content, and more preferably 6.0 ~ 8%.
Have according to lactam monomers of the present invention and to elect in hexanolactam, oenantholactam, 11 lactan, the laurolactam any one as.More preferably hexanolactam, oenantholactam.
For the productive rate and the shortening preparation time that further increase branched chain nylon resin, described step b) is specially:
B1) add successively institute's polymerization single polymerization monomer, properties-correcting agent, catalyzer in the reactor, fasten feeding cover, connect the jacket of polymerization water coolant, making the still internal pressure with the high pure nitrogen pressurising is 0.2Mpa ~ 0.5Mpa, open relief valve and vacuumize, make the still pressure drop to-0.03Mpa ~-0.05Mpa, so operation is for several times, logical high pure nitrogen is fastened vent valve again to normal pressure at last;
B2) with the heating of described reactor, when temperature reaches 80 ℃ of left and right sides, to open and stir, stir speed (S.S.) is controlled between 60rpm ~ 240rpm, is warming up to 200 ~ 260 ℃, and caprolactam monomer carries out ring-opening reaction, after the reaction times is 1.0-4 hour,
Step c) is specially: enter vacuum polymerization, vacuum is-0.02-0.08Mpa temperature: 250-280 ℃, the time is 2-4 hour, enters molecular balance again, and compound temperature is 260-280 ℃, and the time is 1.0-2.0 hour.Can finish polymerization, discharging is cut and is drawn, extracts, dry, packing.
Below in conjunction with example in detail the present invention, but the present invention has more than and is confined to following instance.
Among the present invention, selected ring opening catalyst can be phosphoric acid, hexosamine or kilnitamin.Hexosamine mixes use with phosphoric acid ester.The implementation step:
1, hexanolactam, catalyzer, cladodification properties-correcting agent are added polymeric kettle, heating and melting by aforementioned ratio.And be warmed up to 230 ℃
2, when temperature rises to 230 ℃, begin to stir.
3, when temperature of reaction to 240 ℃, note control temperature (240 ℃-260 ℃), the reaction times is about 5 hours.
4, reaction began to vacuumize after 5 hours.Vacuum degree control more than 0.06MPa, under vacuum successive reaction 2-4 hour.
5, after balance certain hour such as 1-2 hour, the discharging pelletizing, and sample preparation detects various performances.The below enumerates several catalyzer application examples and existing hydrolysis process compares:
Table 1 embodiment and comparison example material formula table (unit: kg)
Table 2 example skill condition
List in table 3 by table 1, table 2 result of implementation:
The unmodified resin the performance test results of table 3 embodiment and comparison example
Consolidated statement 2 and as seen from Table 3, example and Comparative Examples comparison shows that: adopt the embodiment synthesis technique of new catalytic auxiliary agent guaranteeing under the basically identical prerequisite of branched chain nylon resin performance, the polymerization process temperature reduces about 20-30 ℃, polymerization reaction time shortens about 6h, and the polymerization process system is without pressure.The new synthetic process of this branch chain nylon has broad application prospects in commercial process because the aspect has fairly obvious advantage reducing energy consumption, reduce production costs, enhance productivity etc.
More than the preparation method of a kind of branched chain nylon resin provided by the invention is described in detail; having used specific examples herein sets forth principle of the present invention and embodiment; the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; should be understood that; for those skilled in the art; under the prerequisite that does not break away from the principle of the invention; can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (8)
1. the preparation method of a branched chain nylon resin is characterized in that, comprising:
Caprolactam monomer, catalyzer and properties-correcting agent are mixed to get mixture and obtain side chain nylon after carrying out ring-opening reaction under 200-260 ℃.
2. preparation method according to claim 1 is characterized in that, described catalyzer is phosphoric acid, phosphoric acid ester, phosphorous acid ester and amino acid whose one or more mixture.
3. preparation method according to claim 1 is characterized in that, described cladodification properties-correcting agent is any one in Amino Terminated polyether(ATPE) compound, end carboxyl polyether compound, polyethyleneimine: amine compound and the Amino Terminated polyether(ATPE)/polymine mixing cpd.
4. preparation method according to claim 1 is characterized in that, described phosphoric acid ester
General formula is: R
3PO
4,
Wherein R is hydrogen, and the carbon atom number is the alkyl of 1-18 or the phenyl of I formula institute formula
R
1It is 1 ~ 10 alkyl for hydrogen or carbon atom number.
5. preparation method according to claim 1 is characterized in that, described amino acid has structure shown in the formula II
R wherein
2It is 6 ~ 12 alkyl for the carbon atom number.
6. preparation method according to claim 1 is characterized in that, described catalyst loading is 0.1 ~ 5% of lactam monomers molar content.
7. preparation method according to claim 1 is characterized in that, described cladodification agent addition is 1.0 ~ 5% of lactam monomers molar content.
8. preparation method according to claim 1 is characterized in that, temperature of reaction is 200-260 ℃, and reaction pressure is normal pressure, and the reaction times is 8-10 hour.
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| CN2012105246973A CN102964589A (en) | 2012-12-07 | 2012-12-07 | Preparation method of branched nylon resin |
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| CN2012105246973A CN102964589A (en) | 2012-12-07 | 2012-12-07 | Preparation method of branched nylon resin |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104130570A (en) * | 2014-07-01 | 2014-11-05 | 浙江俊尔新材料股份有限公司 | Polyamide composite material, preparation method thereof, and application thereof to prepare automobile door handles |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1153232A (en) * | 1996-11-04 | 1997-07-02 | 岳阳石油化工总厂研究院 | Method for producing nylon 6 using hexanolactam oligomer residue |
| US20030149228A1 (en) * | 2000-03-10 | 2003-08-07 | Loontjens Jacobus A | Process for preparing a branched polymer |
| CN102432869A (en) * | 2011-08-15 | 2012-05-02 | 株洲时代新材料科技股份有限公司 | Preparation method of branched chain nylon resin |
-
2012
- 2012-12-07 CN CN2012105246973A patent/CN102964589A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1153232A (en) * | 1996-11-04 | 1997-07-02 | 岳阳石油化工总厂研究院 | Method for producing nylon 6 using hexanolactam oligomer residue |
| US20030149228A1 (en) * | 2000-03-10 | 2003-08-07 | Loontjens Jacobus A | Process for preparing a branched polymer |
| CN102432869A (en) * | 2011-08-15 | 2012-05-02 | 株洲时代新材料科技股份有限公司 | Preparation method of branched chain nylon resin |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104130570A (en) * | 2014-07-01 | 2014-11-05 | 浙江俊尔新材料股份有限公司 | Polyamide composite material, preparation method thereof, and application thereof to prepare automobile door handles |
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Application publication date: 20130313 |