CN104592512A - Carbon dioxide based polyurea and preparation method and application thereof - Google Patents
Carbon dioxide based polyurea and preparation method and application thereof Download PDFInfo
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- CN104592512A CN104592512A CN201510086431.9A CN201510086431A CN104592512A CN 104592512 A CN104592512 A CN 104592512A CN 201510086431 A CN201510086431 A CN 201510086431A CN 104592512 A CN104592512 A CN 104592512A
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Abstract
The invention discloses carbon dioxide based polyurea and a preparation method and application thereof, belongs to the technical field of macromolecular materials, and solves the technical problem in the prior art that the molecular weight of the carbon dioxide based polyurea prepared by the preparation method of the carbon dioxide based polyurea is low, so that the carbon dioxide based polyurea cannot be further applied. The method comprises the following steps: adding a prepolymer or a sliced prepolymer in a reaction device, then continuously blowing carbon dioxide into the reaction device, and completely reacting amino in the prepolymer so as to generate the carbon dioxide based polyurea, wherein the reaction temperature is 120-400 DEG C, the reaction pressure is 0.1-20 MPa, and the reaction time is 0.5-50h. The carbon dioxide which is continuously blown in the method not only can take away a by-product, water, which is not eliminated in the polymerization of the carbon dioxide under a high pressure but also can be inserted into a reaction system, the average molecular weight of the prepared polyurea is between 5000-50000, and the properties are excellent.
Description
Technical field
The present invention relates to a kind of carbon dioxide-base polyureas and preparation method thereof and application, belong to technical field of polymer materials.
Background technology
Polyureas is a kind of macromolecular material with good mechanical property, resistance, thermotolerance, machine-shaping can be carried out by plastic film mulch, injection moulding, the mode such as to extrude, can be used as fiber, lubricant, film, engineering plastics, elastomerics and coating etc.Existing polyureas preparation method mainly passes through diamines or polyamines and isocyanate reaction and is formed, but isocyanic ester toxicity is comparatively large, so working method has a strong impact on HUMAN HEALTH.
In order to solve the problems of the technologies described above, Chinese patent (publication number 102432871A) discloses a kind of preparation method of polyureas, adopts aminated compounds and excessive CO
2condensation reaction is carried out, one-step synthesis polyureas in airtight reaction vessel.The method does not rely on isocyanic ester, reduces the pollution to HUMAN HEALTH and environment, but polyureas molecular weight prepared by the method is lower, and then causes the polyureas performance of preparation on the low side, cannot apply.
Summary of the invention
The object of the invention is to solve the carbon dioxide-base polyureas molecular weight that in prior art prepared by carbon dioxide-base polyureas preparation method low, the technical problem that cannot apply further, provides a kind of carbon dioxide-base polyureas and preparation method thereof and application.
The invention provides a kind of preparation method of carbon dioxide-base polyureas, comprise the following steps:
Step one, carbaminate or multiamino compound are added in reaction unit, after airtight, purge carbonic acid gas 1-10min in reaction unit after, keep carbonic acid gas under 0.8-5MPa constant pressure, be warming up to 120-260 DEG C, under keeping steady temperature, raised pressure is to 5-30MPa, under air-tight state, polycondensation 0.5-48h, obtains prepolymer;
In described step one, the structural formula of carbaminate is
In formula, R is aliphatic carbon chain, aromatic carbon chains or semi-aromatic carbochain;
Described multiamino compound is one or more in aliphatic polyamine, aromatic polyamine, alicyclic polyamine, Amino End Group oligopolymer;
Step 2, the prepolymer that step one obtained are directly or add in reaction unit after section, then continue to purge carbonic acid gas in reaction unit, amino in prepolymer reacts completely, generate carbon dioxide-base polyureas, temperature of reaction is 120-400 DEG C, reaction pressure is 0.1-20MPa, and the reaction times is 0.5-50h.
Preferably, in described step 2, prepolymer step one obtained directly adds reaction unit, under keeping carbonic acid gas 0.1-20MPa to continue purging, is first warming up to 120-230 DEG C, after stablizing 1-30min, continue to be warming up to 200-400 DEG C, under constant temperature, reaction 25min-49.5h, amino in prepolymer reacts completely, and obtains carbon dioxide-base polyureas;
Preferably, in described step 2, add after the prepolymer chips that step one is obtained in reaction unit, under keeping carbonic acid gas 0.1-20MPa to continue purging, be first warming up to lower than onset melting temperature 30-50 DEG C, after stablizing 1min-15h, continue to be warming up to lower than onset melting temperature 5-25 DEG C, under constant temperature, reaction 25min-49.5h, amino in prepolymer reacts completely, and obtains carbon dioxide-base polyureas.
Preferably, in described step 2, before intensification, carbonic acid gas 0.1-20MPa is kept to continue to purge 1-30min, air in removing device.
Preferably, in described step 2, after the completion of reaction, 0.5-5h is vacuumized.
Preferably, in described step 2, after section, the particle diameter of prepolymer is 0.1um-10cm.
Preferably, described aliphatic polyamine is 1, 4-butanediamine, 1, 5-pentamethylene diamine, 2-methyl 1, 5-pentamethylene diamine, 1, 6-hexanediamine, 1, 7-heptamethylene diamine, 1, 8-octamethylenediamine, 1, 9-nonamethylene diamine, 1, 10-decamethylene diamine, 1, 11-11 methylene diamine, 1, 12-ten dimethylene diamines, 1, 13-ten trimethylene diamine, 1, 14-ten tetramethylene-diamine, 1, 15-ten five methylene diamine, 1, 16-ten hexamethylene-diamine, 1, 17-ten heptamethylene diamines, 1, 18-18 methylene diamine, piperazine, Amino Terminated polyether(ATPE), Amino End Group polythioether, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, polyethylene polyamine, lauryl amine dipropylenediamine, N, the sub-dipropyl triamine of N-dimethyl, three aminomethyl amine, three aminopropyl amine, triaminotriethylamine, 2, 4, 4-trimethylhexane diamine, 2, 2, 4-trimethylhexane diamine, isophorone diamine, 2-methyl isophthalic acid, one or more in 5 pentamethylene diamines,
Described aromatic polyamine be p dimethylamine, m-xylene diamine, O-phthalic amine, to benzene diethylamine, isophthalic diethylamine, adjacent benzene diethylamine, 4,4'-(1,4-benzene dioxy base) dianiline, 4,4'-(1,4-benzene dioxy base) two benzene methanamine, 4,4'-(Isosorbide-5-Nitrae-benzene dioxy base) two phenylethylamine, 3, one or more in 3'-diaminobenzidine, benzidine, 2,2'-bis-(trifluoromethyl) benzidine, tolylene diamine;
Described Amino End Group oligopolymer is Amino End Group polyamide oligomer, Amino End Group polyimide oligomer, Amino End Group polyester oligomer, amino-terminated polyurethane oligopolymer, Amino End Group polyureas oligopolymer, Amino End Group polycarbonate oligomer, Amino Terminated polyether(ATPE) sulfone oligopolymer, Amino End Group polyolefin oligomer, Amino End Group polyphenylene sulfide oligopolymer, Amino End Group polysiloxane oligomer, Amino Terminated polyether(ATPE) ketone oligopolymer, Amino Terminated polyether(ATPE) ketone oligopolymer, Amino End Group polyoxymethylene oligopolymer, Amino End Group polyaniline oligomer, Amino End Group linear phenolic resin oligopolymer, Amino End Group linear loop epoxy resins oligopolymer, Amino End Group polyolefin oligomer, Amino End Group polysiloxane oligomer, Amino Terminated polyether(ATPE) oligopolymer, Amino Terminated polyether(ATPE) ether ketone oligopolymer, one or more in Amino End Group polyaryletherketone oligopolymer.
Preferably, in described step one, when polyamine compounds is 1, 4-butanediamine, 1, 5-pentamethylene diamine, 2-methyl 1, 5-pentamethylene diamine, 1, 6-hexanediamine, 1, 7-heptamethylene diamine, 1, 8-octamethylenediamine, 1, 9-nonamethylene diamine, 1, 10-decamethylene diamine, 1, 11-11 methylene diamine, 1, 12-ten dimethylene diamines, 1, 13-ten trimethylene diamine, 1, 14-ten tetramethylene-diamine, 1, 15-ten five methylene diamine, 1, 16-ten hexamethylene-diamine, 1, 17-ten heptamethylene diamines or 1, during 18-18 methylene diamine, before step one purges carbonic acid gas in reaction unit, also in reaction unit, add diacid, one or more in dicarboxylic anhydride.
Preferably, in described step 2, before purging carbonic acid gas, also in reaction unit, add end-capping reagent and/or catalyzer, described end-capping reagent is unary primary amine, unitary secondary amine, monoprotic acid, unitary acid anhydrides, unitary acyl chlorides, unitary isocyanic ester, unitary epoxy compounds or ketone compounds; Described catalyzer is sodium hydroxide, magnesium hydroxide, cesium hydroxide, calcium oxide, magnesium oxide, zirconium white, metal carbonate, alkali metal bicarbonate salt, alkaline molecular sieve, alkaline exchange of particles resin, tertiary amine compounds, alkali ionic liquid, alkaline polymer sulfuric acid, hydrochloric acid, nitric acid, protonic acid, Lewis acid, aliphatic diacid or aromatic diacid.
The present invention also provides the preparation method of above-mentioned carbon dioxide-base polyureas the carbon dioxide-base polyureas prepared, and the number-average molecular weight of this carbon dioxide-base polyureas is at 5000-50000.
The present invention also provides the application of above-mentioned carbon dioxide-base polyureas: by carbon dioxide-base polyureas and additive 100:(1-100 in mass ratio) blended, mixed by twin-screw extrusion or mechanical stirring, after dicing machine granulation, obtain the polyurea matrix resin of modification;
Described additive is one or more in softening agent, toughner, chemical stabilizer, coupling agent, antioxidant, photostabilizer, defoamer, mould inhibitor, static inhibitor, thinner, tinting material, dispersion agent, rheological agent, anti-sedimentation agent, weighting agent, whipping agent, acidifying preventing agent, fire retardant, flame retardant, thermo-stabilizer, fibrous supporting material, packing material, pigment.
The present invention also provides a kind of application of above-mentioned carbon dioxide-base polyureas: by carbon dioxide-base polyureas and intermingling material 100:(1-100 in mass ratio) blended, mixed by twin-screw extrusion or mechanical stirring, after dicing machine granulation, obtain blending resin;
Described intermingling material is polyphenylene oxide, polyphenylene sulfide, polyester, polymeric amide, polycarbonate, poly(lactic acid), urethane, isocyanate-based polyureas, polyethersulfone, polyethylene, polypropylene, polystyrene, polypyrrole, Polythiophene, tetrafluoroethylene or polyvinyl chloride.
The present invention also provides the application of another kind of above-mentioned carbon dioxide-base polyureas: by carbon dioxide-base polyureas through melt-spinning, solvent spinning or electrostatic spinning, obtain polyurea fiber.
Compared with prior art, beneficial effect of the present invention:
1, carbon dioxide-base polyureas of the present invention adopts prepolymer to generate polyureas with the carbon dioxide reaction continuing to purge, the polyureas number-average molecular weight not only prepared is between 5000-50000, excellent performance, possess good mechanical property and thermostability, Young's modulus can reach 1.1GPa, and tensile strength can reach 52.5MPa, elongation at break is 55%, fusing point is 110-300 DEG C, and preparation process environmental protection, free from environmental pollution;
2, the present invention is in the reaction process of prepolymer with the lasting carbonic acid gas purged, the carbonic acid gas continuing to purge can take away the water byproduct that carbonic acid gas is not got rid of in high pressure polymerisation on the one hand, prevent water byproduct from causing the hydrolysis reaction of polyureas, eliminate prepolymer be polymerized with CO 2 high pressure and the process that removes water byproduct under high pressure conditions restricts mutually, guarantee high pressure polymerisation carries out smoothly; On the other hand, the polarity overcome due to Liquid carbon dioxide or supercritical co is less, and the urea groups polarity in polyureas is very strong, the carbonic acid gas small molecules insertion reaction system difficulty caused, mass transfer difficulty, for prepolymer generates the carbonic acid gas that high molecular polyureas provides abundance;
3, the present invention prepares carbon dioxide-base polyureas and by blended with multiple additives, can obtain the carbon dioxide-base polyureas of modification; Also can be blended with various kinds of resin, obtain blended carbon dioxide-base polyureas; Can also fiber sprinning be passed through, prepare carbon dioxide-base polyurea fiber.
Accompanying drawing explanation
Fig. 1 is the FTIR spectrum of polyureas prepared by embodiment 1;
Fig. 2 is the substance assistant laser desorpted ionized mass spectrum of polyureas prepared by embodiment 1;
Fig. 3 is the differential scanning calorimetric curve of polyureas prepared by embodiment 1.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiments of the invention are described, but should be appreciated that these describe just to further illustrate the features and advantages of the present invention instead of limiting to the claimed invention.
The preparation method of carbon dioxide-base polyureas of the present invention adopts lasting purging carbonic acid gas and prepolymer to react, carbonic acid gas can react with prepolymer, can take away again the water byproduct of reaction, the efficient removal of water inhibits again the hydrolysis reaction of polyureas to occur, and then improves the molecular weight of polyureas.Temperature of reaction is 120-400 DEG C, and reaction pressure is 0.1-20MPa, and the reaction times is 0.5-50h.Concrete grammar can adopt melt polymerization also can adopt solid state polymerization.
The method of melt polymerization: prepolymer is directly added in reaction unit, to in reaction unit, continue to purge carbonic acid gas 1-30min, in removing reaction unit after air, under keeping carbonic acid gas 0.1-20MPa to purge, first be warming up to more than onset melting temperature to 230 DEG C with 1-20 DEG C/min, be generally 120-230 DEG C, stablize 1-30min, in intensification and stabilization process, carbonic acid gas and prepolymer solid state polymerization, and take away water byproduct, continue to be warming up to 200-400 DEG C with 1-20 DEG C/min, 25min-49.5h is reacted under constant temperature, in intensification and reaction process, carbonic acid gas and prepolymer continue melt polymerization, and take away water byproduct, until the amino in prepolymer reacts completely, obtain carbon dioxide-base polyureas, after reaction terminates, can by vacuumizing the remaining water byproduct of removing and other small molecular weight impurity, pumpdown time can be 0.5-5h.
The method of solid state polymerization: after prepolymer being pressed particle diameter 0.1um-10cm section, add in reaction unit, continue to purge carbonic acid gas 1-30min in reaction unit, in removing reaction unit after air, under keeping carbonic acid gas 0.1-20MPa to purge, first be warming up to lower than onset melting temperature 30-50 DEG C with 1-20 DEG C/min, stablize 1-15h, in intensification and stabilization process, carbonic acid gas and prepolymer solid state polymerization, and take away water byproduct, continue to be warming up to lower than onset melting temperature 5-25 DEG C with 1-20 DEG C/min, 25min-49.5h is reacted under constant temperature, in intensification and reaction process, carbonic acid gas and prepolymer solid state polymerization, and take away water byproduct, until the amino in prepolymer reacts completely, obtain carbon dioxide-base polyureas, after reaction terminates, can by vacuumizing the remaining water byproduct of removing and other small molecular weight impurity, pumpdown time can be 0.5-5h.
The temperature of reaction of melt polymerization of the present invention, higher than onset melting temperature, is generally 120-400 DEG C, and lower than 120 degree, prepolymerization is difficult to occur, and higher than 400 DEG C, part polyureas decomposes, and high temperature power consumption is comparatively large, and product is easily oxidized.Consider polymerization efficiency, the preferred 120-300 DEG C of temperature of reaction of the present invention.The temperature of reaction of solid state polymerization is lower than onset melting temperature 5-50 DEG C, and solid state polymerization is generally used for the preparation of the higher polyureas of fusing point.As aliphatie diamine, containing heteroatomic diamines, aliphatie diamine oligopolymer, containing heteroatomic diamines oligopolymer, can adopt melt polymerization, aliphatie diamine and the part semiaromatic diamines of short carbon chain can adopt solid state polymerization.Temperature, pressure control mode specifically can adopt constant temperature and pressure, constant temperature boost and increasing temperature and pressure, by control differing temps and pressure, keep water be vaporous water under corresponding temperature and pressure, can moisture be taken away by the purging of carbon dioxide.The Purge methods of carbonic acid gas does not limit, and can purge, reverse purging, side direction purging etc. for forward.
The purity of carbonic acid gas of the present invention is generally more than 85%, and purity is more high is more conducive to reaction, and preferred purity is more than 99%, and foreign gas can be the rare gas elementes such as nitrogen, argon gas, helium.The carbonic acid gas discharged in the carbonic acid gas that commercially available carbonic acid gas, carbon material specifically can be adopted to burn or factory's flue.
The preparation method of prepolymer of the present invention is:
Carbaminate or multiamino compound are added in reaction unit, after airtight, purge carbonic acid gas 1-10min in reaction unit after, keep carbonic acid gas under 0.8-5MPa constant pressure, be warming up to 120-260 DEG C, under keeping steady temperature, raised pressure is to 5-30MPa, under air-tight state, polycondensation 0.5-48h, obtains prepolymer.
Wherein, the structural formula that carbaminate is is
in formula, R is aliphatic carbon chain, aromatic carbon chains or semi-aromatic carbochain; Aliphatic carbon chain comprises representative examples of saturated aliphatic carbochain (as C
2-C
18alkyl), unsaturated aliphatic carbochain, main chain contain the aliphatic carbon chain of thioether bond (-S-), main chain contains secondary amino group (-NH-) aliphatic carbon chain, main chain contain the aliphatic carbon chain of tertiary amino, the aliphatic carbon chain containing side base, as (CH
2)
1-18, NH-CH
2-CH
2-NH-CH
2-CH
2-NH, HN (CH
2cH
2nH)
2cH
2cH
2nH, HN (CH
2cH
2nH)
3cH
2cH
2nH), poly(propylene oxide), polyethylene oxide etc.
The preparation method of carbaminate can be: be 100:(2 ~ 500 by mass ratio) organic amine and organic solvent add in reaction unit, stir, at-10 DEG C ~ 100 DEG C, under Keep agitation, in reaction unit, be filled with CO
2gas, gaseous tension in reaction unit is made to reach 0.1MPa ~ 15MPa, after reaction 2min ~ 10h, removing organic solvent, namely carbaminate is obtained, organic solvent can be one or more the mixing in water, methyl alcohol, ethanol, Virahol, the trimethyl carbinol, propyl carbinol, acetone, ethyl acetate, succinate, dioxane, tetrahydrofuran (THF), toluene, acetonitrile, chlorobenzene, N-Methyl pyrrolidone (NMP) and 1,3-DMPU (DMPU), organic amine can be quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, 1, 2-propylene diamine, 1, 4-butanediamine, 1, 5-pentamethylene diamine, 1, 6-hexanediamine, 1, 7-heptamethylene diamine, 1, 8-octamethylenediamine, 1, 9-nonamethylene diamine, 1, 10-decamethylene diamine, 1, 11-11 methylene diamine, 1, 12-dodecyl diamines, 1, 13-tridecyl diamines, 1, 14-tetradecanediamine, 1, 15-pentadecyl diamines, 1, 16-hexadecyl diamines, 1, 4-cyclohexanediamine, 4, the own methylene diamine of 4 '-methyl bicyclic, Ursol D, mphenylenediamine, polyureas, polycyclic oxygen second methylene diamine, polycyclic oxygen third methylene diamine, one or more mixing in Amino End Group polysiloxane.
Wherein, multiamino compound is one or more in aliphatic polyamine, aromatic polyamine, alicyclic polyamine, Amino End Group oligopolymer;
Aliphatic polyamine is one or more in following compound:
(1) Amino End Group C
4-C
18aliphatic carbon chain diamines, Amino End Group can be primary amine or secondary amine, as: Putriscine, 1,5-pentamethylene diamine, 2-methyl 1,5-pentamethylene diamine, 1,6-hexanediamine, 1,7-heptamethylene diamine, 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 1,10-decamethylene diamine, 1,11-ten one methylene diamine, 1,12-ten dimethylene diamines, 1,13-ten trimethylene diamine, 1,14-ten tetramethylene-diamine, 1,15-ten five methylene diamine, 1,16-ten hexamethylene-diamine, 1,17-ten heptamethylene diamines, 1,18-ten eight methylene diamine, piperazine etc.;
(2) Amino End Group aliphatic carbon chain triamine or tetramine: end contains the multiamino compound that the multiamino compound of three Amino End Group or end contain four Amino End Group;
(3) main chain contains the aliphatics multiamino compound of heteroatoms or unsaturated link(age), as:
A, main chain contain the aliphatics multiamino compound of ehter bond (-O-), as: Amino Terminated polyether(ATPE);
B, main chain contain the aliphatics multiamino compound of thioether bond (-S-), as: Amino End Group polythioether;
C, main chain contain the aliphatics multiamino compound of secondary amino group (-NH-), as: polyethylene polyamine comprises diethylenetriamine, triethylene tetramine, tetraethylene pentamine, polyethylene polyamine, lauryl amine dipropylenediamine, the sub-dipropyl triamine of N, N-dimethyl;
D, main chain contain the aliphatics multiamino compound of tertiary amino, as: three aminomethyl amine, three aminopropyl amine, triaminotriethylamine;
E, unsaturated aliphatic multiamino compound: containing one or more unsaturated link(age) containing in the main carbochain of Amino End Group or on side chain, as carbon-carbon double bond, carbon carbon triple bond, carbon-to-nitrogen double bon etc.;
(4) carbochain contains the aliphatics multiamino compound of one or more sides base, or containing heteroatomic aliphatics multiamino compound in the base of side, specifically broken down as follows:
A, side base are carbochain or alicyclic radical (-C
nh
2n+1, wherein n is the integer of 1-10, comprises all kinds of isomer), as 2,4,4-trimethylhexane diamine, 2,2,4-trimethylhexane diamine, isophorone diamine, 2-methyl isophthalic acid, 5 pentamethylene diamines;
B, side base are halogen (-F ,-Cl ,-Br ,-I), alkoxyl group, sulfydryl etc., siloxy, in the base of side, also can comprise alkyl and other groups simultaneously.
Aromatic multi-amine, semiaromatic polyamines, the general structure of alicyclic polyamine is as follows:
In formula I, phenyl ring can replace with the one in following structure, and two Amino End Group can replace at an arbitrary position:
In formula II,
represent the one in following structure;
Wherein, Y represents H or halogen, and X represents H or halogen;
As m1=m2=0, what formula I and formula II represented be aromatic multi-amine, and two Amino End Group can optional position replacement on ring, other can the substituting group of the position of substitution (as R
1, R
2, R
3, R
4, R
1', R
2', R
3', R
4') be any substituting group, as: hydrogen atom, halogen, alkyl, alkoxyl group, hydroxyl, sulfydryl;
When m1, m2 are the integer of 1-12, what formula I and formula II represented be semiaromatic polyamines, and two Amino End Group can optional position replacement on ring, other can the substituting group of the position of substitution (as R
1, R
2, R
3, R
4, R
1', R
2', R
3', R
4') can be hydrogen atom, halogen, alkyl, alkoxyl group, hydroxyl, sulfydryl.As p dimethylamine, m-xylene diamine, O-phthalic amine, to benzene diethylamine, isophthalic diethylamine, adjacent benzene diethylamine, 4,4'-(1,4-benzene dioxy base) dianiline, 4,4'-(1,4-benzene dioxy base) two benzene methanamine, 4,4'-(Isosorbide-5-Nitrae-benzene dioxy base) two phenylethylamine, 3,3'-diaminobenzidine, benzidine, 2,2'-bis-(trifluoromethyl) benzidine, tolylene diamine;
When m1, m2 are the integer of 1-12, when the aromatic nucleus of formula I and formula II is replaced with cycloaliphatic ring, what formula I and formula II represented is alicyclic polyamine, two Amino End Group can optional position on ring replace, and other can the substituting group of the position of substitution can be hydrogen atom, halogen, alkyl, alkoxyl group, hydroxyl, sulfydryl.
At above-mentioned aromatic multi-amine, semiaromatic polyamines, in the general structure of alicyclic polyamine, two Amino End Group substituting groups can be replaced with three Amino End Group substituting groups, the corresponding minimizing of other substituting group one, other conditions are constant.
Wherein, Amino End Group oligopolymer can be Amino End Group polyamide oligomer, Amino End Group polyimide oligomer, Amino End Group polyester oligomer, amino-terminated polyurethane oligopolymer, Amino End Group polyureas oligopolymer, Amino End Group polycarbonate oligomer, Amino Terminated polyether(ATPE) sulfone oligopolymer, Amino End Group polyolefin oligomer, Amino End Group polyphenylene sulfide oligopolymer, Amino End Group polysiloxane oligomer, Amino Terminated polyether(ATPE) ketone oligopolymer, Amino Terminated polyether(ATPE) ketone oligopolymer, Amino End Group polyoxymethylene oligopolymer, Amino End Group polyaniline oligomer, Amino End Group linear phenolic resin oligopolymer, Amino End Group linear loop epoxy resins oligopolymer, Amino End Group polyolefin oligomer, Amino End Group polysiloxane oligomer, Amino Terminated polyether(ATPE) oligopolymer, Amino Terminated polyether(ATPE) ether ketone oligopolymer, one or more in Amino End Group polyaryletherketone oligopolymer.
In the preparation method of polyureas of the present invention, before purging carbonic acid gas, end-capping reagent and/or catalyzer can also be added in reaction unit.Wherein, end-capping reagent can adopt unary primary amine, unitary secondary amine, monoprotic acid, unitary acid anhydrides, unitary acyl chlorides, unitary isocyanic ester, unitary epoxy compounds or ketone compounds, the amount of substance of the terminal functional group in end-capping reagent and the amount of substance of the repeating unit in final polyurea main chain are than being 1:(20-200), end-blocking official can be amino, carboxyl etc.Catalyzer can adopt sodium hydroxide, magnesium hydroxide, cesium hydroxide, calcium oxide, magnesium oxide, zirconium white, metal carbonate, alkali metal bicarbonate salt, alkaline molecular sieve, alkaline exchange of particles resin, tertiary amine compounds, alkali ionic liquid, alkaline polymer sulfuric acid, hydrochloric acid, nitric acid, protonic acid, Lewis acid, aliphatic diacid or aromatic diacid, and the mass ratio of catalyzer and prepolymer is (0.001-1): 100.
The present invention prepares the number-average molecular weight of carbon dioxide-base polyureas between 5000-50000.
Carbon dioxide-base polyureas prepared by the present invention can also further by additive agent modified; concrete grammar is: in the carbon dioxide-base polyureas of 100 weight parts; add the additive of 1-100 weight part; mixed by twin-screw extrusion or mechanical stirring; after dicing machine granulation, obtain the polyurea matrix resin concentrates of modification.Wherein, additive can be one or more in softening agent, toughner, chemical stabilizer, coupling agent, antioxidant, photostabilizer, defoamer, mould inhibitor, static inhibitor, thinner, tinting material, dispersion agent, rheological agent, anti-sedimentation agent, weighting agent, whipping agent, acidifying preventing agent, fire retardant, flame retardant, thermo-stabilizer, fibrous supporting material, packing material, pigment.Wherein, fibrous supporting material can be one or more in glass fibre (as: simple glass fiber, aluminium, magnesium, silicon glass fibre, silicon-aluminum-magnesium lime glass fiber, resurrection glass fibre, quartz glass fibre etc.), the two oxazole fiber of aluminium borate whisker, carbon fiber (high modulus carbon fiber, high-modulus glass fiber), aromatic polyester, aromatic polyamides, superelevation number-average molecular weight polyethylene, polyparaphenylene benzo, carbon whisker, silicon carbide fiber, silicon nitride fiber, sapphire whisker.Packing material can be swelling clay, metal oxide and composition thereof, metal oxide compounds (as polynite, diatomite, calcite, uhligite etc.), metallic sulfide, metallic carbide, non-metallic carbide, metal-powder and composition thereof, hollow glass microbead, the various allotropic substance of non-metal simple-substance (as carbon black, acetylene black, decolorizing carbon, graphite, Graphene and oxide compound thereof, sulphur powder etc.).Above-mentioned packing material can be the structures such as carbon nanotube, nano wire, nanometer rod, nanoparticle, is not particularly limited.Coupling agent can be one or more in silane coupling agent, titante coupling agent, and coupling agent has polarity and assists immersional wetting, can improve the affinity of fibrous supporting material or packing material and polyureas.Pigment can be one or more in titanium dioxide, carbon black, ultramarine pigment, white dyes.Fire retardant can for containing halogen compounds, the compound of antimonous oxide, trimeric cyanamide compounds, as, the bromide of chloro thing-sb oxide system, low number-average molecular weight or high number-average molecular weight-sb oxide system, red phosphorus, phosphorus compound, metal hydrate, boride, stannide.Softening agent can be phenolic compound, dimethyl phthalate, phenyl-phosphate compounds, the polyvalent alcohol of N-alkyl benzene sulfonamide class sulfonamide compounds, P-hydroxybenzoic acid monooctyl ester, octyl cresol etc.Toughner can be natural rubber, synthetic rubber, modified natural rubber or modified synthetic rubber, and such as ethylene-propylene rubber(EPR), by after the functional modification of glycidyl methacrylate, can improve the reactivity to polyureas; Also can using the grafts of acrylic copolymer less for particle diameter, the ethylene-dien terpolymer containing hydroxyl, the ethylene-dien terpolymer containing epoxy group(ing), emulsion polymerized elastomeric body containing polymers of carboxylic acid, containing sour elastomerics with to mix in polyureas as disperse phase containing acid anhydrides elastomerics and strengthen its toughness.
Carbon dioxide-base polyureas prepared by the present invention can also further with other resin alloy modifications, concrete grammar is: be 100:(1-100 in mass ratio by polyurea matrix resin concentrates and the intermingling material of the carbon dioxide-base polyureas of preparation or above-mentioned modification) mixed by twin-screw extrusion or mechanical stirring, after dicing machine granulation, obtain blended carbon dioxide-base polyureas, wherein, intermingling material comprises polyphenylene oxide, polyphenylene sulfide, polyester, acryl butadiene styrene multipolymer, polymeric amide, polycarbonate, poly(lactic acid), urethane, isocyanate-based polyureas, polyethersulfone, polyethylene, polypropylene, polystyrene, polypyrrole, Polythiophene, tetrafluoroethylene, polyvinyl chloride, polyphenylene ether oligomer thing, polyphenylene sulfide oligopolymer, polyester oligomer, polyamide oligomer, polycarbonate oligomer, poly(lactic acid) oligopolymer, polyurethane oligomer, isocyanate-based polyureas oligopolymer, polyethersulfone oligomer, polyethylene oligopolymer, polypropylene oligopolymer, polystyrene oligopolymer, polypyrrole oligopolymer, Polythiophene oligopolymer, tetrafluoroethylene oligopolymer, polyvinyl chloride oligopolymer.As polyureas-6 and nylon 6 mixing.
Reaction unit of the present invention: in melt polymerization, reaction unit generally adopts hugging formula reactor; In solid state polymerization, reaction unit generally adopts solid phase reactor, as: ebullated bed solid phase reactor, fluidized-bed solid phase reactor, ridge type solid phase reactor etc.Prepare in the preparation method of prepolymer, reaction unit can adopt High Temperature High Pressure mechanic whirl-nett reaction still, and whipping appts does not have particular requirement.
Below in conjunction with preferred version, further illustrate the preparation method of polyureas of the present invention:
1, method of the present invention can prepare alcohol dissolubility polyureas:
Alcohol dissolubility polyureas can be prepared when the many ammoniates adopted are mixture or the polycomponent Amino End Group polyamide oligomer of polycomponent diamines.As octamethylenediamine, decamethylene diamine, ten dimethylene diamines and carbon dioxide copolymerization can prepare alcohol dissolubility polyureas; The Amino End Group prepolymer of hexanolactam/nylon salt, the Amino End Group oligopolymer of nylon 6/66/610, the Amino End Group oligopolymer of nylon 6/66PACM6, Amino End Group oligopolymer and the carbonic acid gas of nylon 6/66/610/12 carry out being polymerized can prepare alcohol dissolubility polyureas.The principal feature of alcohol dissolubility polyureas dissolves in methyl alcohol, ethanol, propyl alcohol and other lower aliphatic alcohols, and in these alcohol, add the mixed solvent of a small amount of moisture, trieline, chloroform, tetracol phenixin, phenylcarbinol, formic acid and acetic acid, be also the good solvent of multi-component Copolymerization nylon.In addition, add softening agent in alcohol dissolubility polyureas after, except making except the character of these resins is improved, dissolution rate, the muddiness of postponing solution or gelation time is being accelerated and is improving have good result in the gumminess of base material etc.Softening agent used mainly contains phenolic compound, dimethyl phthalate, phenyl-phosphate compounds and the polyvalent alcohol of N-alkyl benzene sulfonamide class sulfonamide compounds, P-hydroxybenzoic acid monooctyl ester, octyl cresol etc.Alcohol dissolubility copolymerization polyureas can carry out blending modification with epoxy resin, resol, urethane, rosin, melamine resin, urea-formaldehyde resin and soluble cotton etc.The method of polymer blend, usually with the alcoholic solution of solubility copolymerization polyureas, mixes with the alcohol of corresponding resin or halohydrocarbon solution.
2, the preparation of unsaturated polyureas: when the multiamino compound adopted is the multiamino compound containing unsaturated link(age), unsaturated polyureas can be obtained.Unsaturated link(age) in unsaturated polyureas can carry out with other unsaturated olefins the heat curing-type polyurea materials that copolymerization prepares good thermal stability and mechanical property.
3, there is the preparation of the polyureas of hot melt adhesive effect: when the multiamino compound adopted be ternary component, quaternary component or five-tuple divide above mixture, or when being the Amino End Group polyamide oligomer of multi component copolymerization, the polyureas sizing agent of fusing point more than 100 DEG C can be prepared.Polyureas sizing agent is mainly used in the gluing of clothing, paper and fiber.
4, the preparation of polyureas thermoplastic elastomer: when the multiamino compound adopted is one or more in Amino End Group polyethylene oxide, Amino End Group poly(propylene oxide), Amino End Group polytetrahydrofuran, Amino End Group carbon dioxide-base polycarbonate, Amino End Group carbon dioxide-base polycarbonate oligomer, with one or more in aliphatic polyamine, aromatic polyamine, semi-aromatic polyamines, Amino End Group oligopolymer, during mixing, polyureas thermoplastic elastomer can be prepared.Polyureas thermoplastic elastomer does not rely on the green polyurea elastomer of isocyanic ester, is different from Spray Polyurea Elastomer of the prior art.Flexible pipe and the conveying belt occasions such as machinery and electrical equipment precise part, automobile component, sports goods, rubber hose for medical can be applied to.
5, the preparation of transparent polyureas: when one or more in the aliphatie diamine of employing with pendent alkyl groups, the alicyclic diamine with pendent alkyl groups, with other aliphatie diamines (C
4-C
18), after one mixing in aromatic diamine, semiaromatic diamines (containing corresponding Amino End Group oligopolymer), more transparent polyureas can be prepared with the copolymerization of carbonic acid gas.Also can be transparent polyureas by the block copolymerization polyureas prepared with carbonic acid gas melt blending by non-crystalline copolymer and hemicrystalline homopolymer or similar non-crystalline copolymer.Also polynary polyurea copolymers can be passed through, as aliphatics ternary/quaternary/five-membered copolymer can prepare transparent polyureas.Polyamine compounds as adopted is 2,2,4-trimethylhexane diamine and 2,4,4-trimethylhexane diamine, 4,4 '-diamino-dicyclohexyl methane, 4,4`-diaminocyclohexyl propane, isophorone diamine, 3,3-dimethyl-4,4 '-diamino-dicyclohexyl methyl hydride, 3,6-dimethylamino bicycloheptane, 5,-tertiary butyl mphenylenediamine, naphthalene-2, when mixing, transparent polyureas can be prepared for more than three kinds in 6 diamines, hexanaphthene-Isosorbide-5-Nitrae-diamines.
6, the preparation of fire-retardant polyureas: when containing phosphoric or halogen in the polyamine compounds adopted, can flame-retardant type polyurea be prepared.Or carry out flame-retardant modified to the polyureas prepared.
The purposes of polyureas prepared by the present invention:
1, polyureas of the present invention can be used as sizing agent and coating.Thermoplastic aliphatic's polyureas (C after pulverizing
5-C
16) powder can prepare polyureas powder coating, has good metal bonding performance.The binding agent that wherein prepared by the aliphatic polyurea of Long carbon chain can be widely used in the bonding of fiber, leather, timber, paper.Polyureas can be used as coating, mainly for alcohol dissolubility polyureas or dispersible polyureas, such as can the polyureas of solution organic phase can as potential oil soluble coating, and the polyureas that can disperse very well in water can be used as water-borne coatings.
2, polyureas can be prepared into fiber and used, and concrete spinning technique comprises melt-spinning and solvent spinning and electrostatic spinning.Carbon dioxide-base polyureas (PUC) after spinning can be used as fiber separately, also polyureas blending or other material fibers can carry out blending, as with tynex, poly-propionitrile fiber, polypropylene fibre, trevira etc. carry out blending.In addition, prepared polyurea fiber can make corresponding macrofiber and staple fibre for strengthening other materials, as reinforced polyester, polymeric amide, polycarbonate, carbon dioxide-base polycarbonate, urethane, isocyanate polyurea, polyethersulfone, polyethylene, polypropylene, polystyrene, polypyrrole, Polythiophene, tetrafluoroethylene, polyvinyl chloride, epoxy resin, resol, Synolac, the affinity that suitable coupling agent improves reinforcement and matrix resin can be added.
3, polyureas can be prepared into film and used, can by existing plastic film mulch method, as two-way stretch film forming, unilateral stretching film forming, casting film-forming, spin-coating film etc., prepared polyurea films can make composite film material with the film of other materials, and prepares sandwich structure composite film material by increasing middle layer.
4, the sizing agent, products formed, film, fiber etc. of polyureas can in the industry such as electrical and electronic parts, trolley part material or the various uses such as Industrial materials and family's use.Main application comprises and is applied to various tubing, packaging film, cable sheath, wear-resistant parts, military project aerospace material, and automobile component and 3D print the preparation of goods.
Embodiment 1
40g ten dimethylene diamine carbamate is added in the mechanic whirl-nett reaction still of 100ml, after airtight, purge after 5min through carbon dioxide, keep pressure 1MPa, be warmed up to 180 DEG C, after temperature-stable, raised pressure is to 11MPa, react 9h under air-tight state after, stopped reaction pressure release, obtaining prepolymer is white solid.
After prepolymer chips, cross 20 mesh sieves, getting 25g prepolymer chips adds in solid phase reactor, first after prepolymer chips being purged 10min with carbon dioxide, carbonic acid gas is kept to be under normal pressure continues purging, start heating, first with 10 DEG C/min from room temperature to 180 DEG C, after stablizing 5min, continue to be warming up to 280 DEG C with 1 DEG C/min, keep constant temperature, and keep carbonic acid gas to be that normal pressure continues to purge lower continuation reaction 0.5h, reaction terminates, and decompression vacuum pumping 0.5h, obtains carbon dioxide-base polyureas.
FTIR spectrum detection (ATR) is carried out, as shown in Figure 1, as can be seen from FTIR spectrum, at 3342cm to the polyureas that embodiment 1 obtains
-1there is the N-H stretching vibration peak of the secondary amino group on urea groups in place, 2925cm
-1and 2853cm
-1there is the stretching vibration of methylene radical, at 1610cm
-1there is the stretching vibration of the carbonyl on urea groups in place.Illustrate in polymkeric substance of the present invention to there is urea/ureido functional group and methylene radical structure, embodiment 1 has prepared polyurea polymer really.
Substance assistant laser desorpted ionized analytical reagent composition is carried out to prepolymer prepared by embodiment 1, solvent is deuterated-hexafluoroisopropanol, and matrix is sinapinic acid, and result as shown in Figure 2, can find that repeating unit is 226.6, namely the repeating unit of 12 methylene radical and a urea groups.The number-average molecular weight using deuterated-hexafluoroisopropanol to obtain polyureas as nucleus magnetic hydrogen spectrum is 13500.
Adopt dsc to carry out changes of heat flux test to the polyureas that embodiment 1 obtains, temperature rise rate is 10 DEG C/min, and as shown in Figure 3, the fusing point recording polyureas prepared by embodiment 1 is 209 DEG C to result, and Tc is 179 DEG C.Illustrate that polyureas prepared by the present invention possesses good resistance toheat.
Table 1 is the detected result of the properties of the polyureas of embodiment 1
Embodiment 2
600g nonamethylene diamine is added in the mechanic whirl-nett reaction still of 2L, after airtight, purge after 3min through carbon dioxide, keep pressure 2MPa, be warmed up to 200 DEG C, after temperature-stable, raised pressure is to 12MPa, react 12h under air-tight state after, stopped reaction pressure release, obtaining prepolymer is white solid.
Prepolymer is transferred in hugging formula reactor, after purging 10min with carbon dioxide, carbonic acid gas is kept to be under normal pressure continues purging, start heating, first with 20 DEG C/min from room temperature to 200 DEG C, after stablizing 5min, continue to be warming up to 270 DEG C with 3 DEG C/min, maintenance constant temperature, and keep carbonic acid gas to be after normal pressure continues to purge lower continuation reaction 10h, reaction terminates, cooling pressure release is sealed up for safekeeping, and obtain carbon dioxide-base polyureas, number-average molecular weight is 23000, fusing point is 237 DEG C, and measuring method is identical with embodiment 1.
Embodiment 3
40g trimethylhexane diamine is added in the magnetic stirred autoclave of 100ml, after airtight, purge after 10min through carbon dioxide, keep pressure 1.5MPa, be warmed up to 195 DEG C, after temperature-stable, raised pressure is to 30MPa, react 30h under air-tight state after, stopped reaction pressure release, obtaining prepolymer is white clumpy solid.
After prepolymer chips, cross 20 mesh sieves, getting 25g prepolymer chips adds in solid phase reactor, first after prepolymer chips being purged 10min with carbon dioxide, carbonic acid gas is kept to be under 3MPa continues purging, start heating, first with 20 DEG C/min from room temperature to 150 DEG C, after stablizing 5min, continue to be warming up to 230 DEG C with 1 DEG C/min, keep constant temperature, and keep carbonic acid gas to be that 2MPa continues to purge lower continuation reaction 30h, reaction terminates, decompression vacuum pumping 3h, obtain carbon dioxide-base polyureas, number-average molecular weight is 18500, fusing point is 183 DEG C, measuring method is identical with embodiment 1.
Embodiment 4
40g hexanediamine is added in the mechanic whirl-nett reaction still of 100ml, after airtight, purge after 10min through carbon dioxide, keep pressure 1.2MPa, be warmed up to 220 DEG C, after temperature-stable, raised pressure is to 5MPa, react 24h under air-tight state after, stopped reaction pressure release, obtaining prepolymer is white clumpy solid.
After prepolymer chips, cross 20 mesh sieves, getting 25g prepolymer chips adds in solid phase reactor, first after prepolymer chips being purged 10min with carbon dioxide, carbonic acid gas is kept to be under 9MPa continues purging, start heating, first with 10 DEG C/min from room temperature to 180 DEG C, after stablizing 5min, continue to be warming up to 310 DEG C with 1 DEG C/min, keep constant temperature, and keep carbonic acid gas to be that 9MPa continues to purge lower continuation reaction 12h, reaction terminates, decompression vacuum pumping 1h, obtain carbon dioxide-base polyureas, number-average molecular weight is 12500, fusing point is 301 DEG C, measuring method is identical with embodiment 1.
Embodiment 5
20g 4,7,10-tri-oxygen-1 is added in the magnetic agitation reactor of 50ml, 13-ten trimethylene diamine (being abbreviated as EDR-220), after airtight, purge after 10min through carbon dioxide, keep pressure 1.2MPa, be warmed up to 120 DEG C, after temperature-stable, raised pressure to 12MPa, react 18h under air-tight state after, stopped reaction pressure release, obtaining prepolymer is yellowish sticky look solid.
Prepolymer is transferred in hugging formula reactor, first after prepolymer being purged 10min with carbon dioxide, carbonic acid gas is kept to be under 0.3MPa continues purging, start heating, first with 10 DEG C/min from room temperature to 160 DEG C, after stablizing 5min, continue to be warming up to 220 DEG C with 1 DEG C/min, keep constant temperature, and keep carbonic acid gas to be after the lasting purging of 0.3MPa continues reaction 30h, reaction terminates, decompression vacuum pumping 5h, obtains carbon dioxide-base polyureas, and number-average molecular weight is 15000, fusing point is 110 DEG C, and measuring method is identical with embodiment 1.
Embodiment 6
The mixture (mass ratio is 1:1) of 40g hexanediamine and octamethylenediamine is added in the magnetic agitation reactor of 100ml, after airtight, purge after 10min through carbon dioxide, keep pressure 1.2MPa, be warming up to 210 DEG C, after temperature-stable, raised pressure is to 14MPa, react 24h under air-tight state after, stopped reaction pressure release, obtaining prepolymer is white solid.
Prepolymer is transferred in hugging formula reactor, first after prepolymer being purged 10min with carbon dioxide, carbonic acid gas is kept to be under 3MPa continues purging, first with 20 DEG C/min from room temperature to 200 DEG C, after stablizing 5min, continue progressively to heat up with 2 DEG C/min temperature reaction, treat that temperature rises to 305 DEG C, keep constant temperature, and keep carbonic acid gas to be that 3MPa purges continuation reaction 15h, reaction terminates, decompression vacuum pumping 1.5h, obtain carbon dioxide-base polyureas, number-average molecular weight is 25600, and measuring method is identical with embodiment 1.
Embodiment 7
40g Amino End Group NYLON610 oligopolymer (prepared by excessive hexanediamine and sebacic acid or prepared by excessive hexanediamine and sebacoyl chloride) is added in the magnetic agitation reactor of 100ml, after airtight, purge after 10min through carbon dioxide, keep pressure 1MPa, be warming up to 200 DEG C, after temperature-stable, raised pressure is to 5MPa, react 10h under air-tight state after, stopped reaction pressure release, obtaining prepolymer is white solid.
Prepolymer is transferred in hugging formula reactor, first after prepolymer being purged 10min with carbon dioxide, start heating, under keeping carbonic acid gas 0.3MPa to continue purging, with 20 DEG C/min from room temperature to 230 DEG C, after stablizing 5min, continue to be warming up to 290 DEG C with 3 DEG C/min, keep constant temperature, and keep carbonic acid gas to be continue reaction 15h, reaction end under 0.3MPa continues purging, decompression vacuum pumping 0.75h, obtain carbon dioxide-base polyureas, number-average molecular weight is 27500, and measuring method is identical with embodiment 1.
Embodiment 8
The mixture (mass ratio is 1:1) of 40g hexanediamine and octamethylenediamine is added in the magnetic agitation reactor of 100ml, after airtight, purge after 10min through carbon dioxide, keep pressure 1.2MPa, be warming up to 210 DEG C, after temperature-stable, raised pressure is to 14MPa, react 24h under air-tight state after, stopped reaction pressure release, obtaining prepolymer is white solid.
Prepolymer is transferred in hugging formula reactor, after purging 10min with carbon dioxide, under keeping carbonic acid gas 0.3MPa to continue purging, start heating, first with 20 DEG C/min from room temperature to 200 DEG C, after stablizing 5min, continue to be warming up to 305 DEG C with 2 DEG C/min, keep constant temperature, and keep carbonic acid gas to be continue reaction 15h, reaction end under 3MPa continues purging, decompression vacuum pumping 1.5h, obtain carbon dioxide-base polyureas, number-average molecular weight is 25020, and measuring method is identical with embodiment 1.
Embodiment 9
40g hexanediamine is added in the magnetic agitation reactor of 100ml, after airtight, purge after 10min through carbon dioxide, keep pressure 1.5MPa, be warming up to 230 DEG C, after temperature-stable, raised pressure is to 15MPa, react 10h under air-tight state after, stopped reaction pressure release, obtaining prepolymer is white solid.
After prepolymer chips, cross 20 mesh sieve, getting 25g prepolymer chips adds in solid phase reactor, after carbon dioxide reverse purging 10min, under keeping carbonic acid gas 1.5MPa to continue reverse purging, start heating, first with 20 DEG C/min from room temperature to 225 DEG C, after reaction 15h, continue to be warming up to 305 DEG C with 10 DEG C/min, keep constant temperature, and keep carbonic acid gas to be that 3MPa continues reverse purging continuation reaction 15h, reaction terminates, decompression vacuum pumping 0.5h, obtain carbon dioxide-base polyureas, number-average molecular weight is 14584, measuring method is identical with embodiment 1.
Embodiment 10
40g octamethylenediamine is added in the magnetic agitation reactor of 100ml, after airtight, purge after 10min through carbon dioxide, keep pressure 1.5MPa, be warming up to 220 DEG C, after temperature-stable, raised pressure is to 12MPa, react 10h under air-tight state after, stopped reaction pressure release, obtaining prepolymer is white solid.
Prepolymer is carried out 8 mesh sieve of cutting into slices, getting 25g prepolymer chips adds in solid phase reactor, after carbon dioxide reverse purging 10min, under keeping carbonic acid gas 0.1MPa to continue forward purging, start heating, first with 20 DEG C/min from room temperature to 180 DEG C, after reaction 3h, continue to be warming up to 230 DEG C with 10 DEG C/min, keep constant temperature, and after keeping carbonic acid gas 0.1MPa forward to continue to purge lower continuation reaction 10h, reaction terminates, and obtain carbon dioxide-base polyureas, number-average molecular weight is 26423, fusing point is 238 DEG C, and measuring method is identical with embodiment 1.
Embodiment 11
35g ten dimethylene diamines is added in the magnetic agitation reactor of 100ml, after airtight, purge after 10min through carbon dioxide, keep pressure 0.8MPa, be warming up to 195 DEG C, after temperature-stable, raised pressure is to 9MPa, react 18h under air-tight state after, stopped reaction pressure release, obtaining prepolymer is white solid.
100 mesh sieve are crossed by after prepolymer chips, getting 25g prepolymer chips adds in solid phase reactor, after carbon dioxide reverse purging 10min, under keeping carbonic acid gas 1.2MPa side direction to continue purging, start heating, first with 20 DEG C/min from room temperature to 190 DEG C, after reaction 10h, continue to be warming up to 200 DEG C with 1 DEG C/min, keep constant temperature, and after keeping carbonic acid gas 1.8MPa to continue side direction purging lower continuation reaction 20h, reaction terminates, and obtain carbon dioxide-base polyureas, number-average molecular weight is 14530, fusing point is 209 DEG C, and measuring method is identical with embodiment 1.
Obviously, the explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that the those of ordinary skill for described technical field, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (13)
1. the preparation method of carbon dioxide-base polyureas, is characterized in that, comprises the following steps:
Step one, carbaminate or multiamino compound are added in reaction unit, after airtight, purge carbonic acid gas 1-10min in reaction unit after, keep carbonic acid gas under 0.8-5MPa constant pressure, be warming up to 120-260 DEG C, under keeping steady temperature, raised pressure is to 5-30MPa, under air-tight state, polycondensation 0.5-48h, obtains prepolymer;
In described step one, the structural formula of carbaminate is
In formula, R is aliphatic carbon chain, aromatic carbon chains or semi-aromatic carbochain;
Described multiamino compound is one or more in aliphatic polyamine, aromatic polyamine, alicyclic polyamine, Amino End Group oligopolymer;
Step 2, the prepolymer that step one obtained are directly or add in reaction unit after section, then continue to purge carbonic acid gas in reaction unit, amino in prepolymer reacts completely, generate carbon dioxide-base polyureas, temperature of reaction is 120-400 DEG C, reaction pressure is 0.1-20MPa, and the reaction times is 0.5-50h.
2. the preparation method of carbon dioxide-base polyureas according to claim 1, it is characterized in that, in described step 2, prepolymer step one obtained directly adds reaction unit, under keeping carbonic acid gas 0.1-20MPa to continue purging, first be warming up to 120-230 DEG C, after stablizing 1-30min, continue to be warming up to 200-400 DEG C, under constant temperature, reaction 25min-49.5h, the amino in prepolymer reacts completely, and obtains carbon dioxide-base polyureas.
3. the preparation method of carbon dioxide-base polyureas according to claim 1, it is characterized in that, in described step 2, add after the prepolymer chips that step one is obtained in reaction unit, under keeping carbonic acid gas 0.1-20MPa to continue purging, first be warming up to lower than onset melting temperature 30-50 DEG C, after stablizing 1min-15h, continue to be warming up to lower than onset melting temperature 5-25 DEG C, under constant temperature, reaction 25min-49.5h, the amino in prepolymer reacts completely, and obtains carbon dioxide-base polyureas.
4. the preparation method of the carbon dioxide-base polyureas according to Claims 2 or 3, is characterized in that, in described step 2, before intensification, keeps carbonic acid gas 0.1-20MPa to continue to purge 1-30min, air in removing device.
5., according to the preparation method of the carbon dioxide-base polyureas of claim 1-3 described in any one, it is characterized in that, in described step 2, after the completion of reaction, vacuumize 0.5-5h.
6. the preparation method of the carbon dioxide-base polyureas according to claim 1 or 3, is characterized in that, in described step 2, after section, the particle diameter of prepolymer is 0.1um-10cm.
7., according to the preparation method of the carbon dioxide-base polyureas of claim 1-3 described in any one, it is characterized in that, described aliphatic polyamine is Putriscine, 1,5-pentamethylene diamine, 2-methyl 1,5-pentamethylene diamine, 1,6-hexanediamine, 1,7-heptamethylene diamine, 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 1，10-diaminodecane, 1,11-11 methylene diamine, 1,12-ten dimethylene diamines, 1,13-ten trimethylene diamine, 1,14-ten tetramethylene-diamine, 1,15-ten five methylene diamine, 1,16-ten hexamethylene-diamine, 1,17-ten heptamethylene diamines, 1,18-18 methylene diamine, piperazine, Amino Terminated polyether(ATPE), Amino End Group polythioether, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, polyethylene polyamine, lauryl amine dipropylenediamine, the sub-dipropyl triamine of N, N-dimethyl, three aminomethyl amine, three aminopropyl amine, triaminotriethylamine, 2,4,4-trimethylhexane diamine, 2,2,4-trimethylhexane diamine, isophorone diamine, 2-methyl isophthalic acid, one or more in 5 pentamethylene diamines,
Described aromatic polyamine be p dimethylamine, m-xylene diamine, O-phthalic amine, to benzene diethylamine, isophthalic diethylamine, adjacent benzene diethylamine, 4,4'-(1,4-benzene dioxy base) dianiline, 4,4'-(1,4-benzene dioxy base) two benzene methanamine, 4,4'-(Isosorbide-5-Nitrae-benzene dioxy base) two phenylethylamine, 3, one or more in 3'-diaminobenzidine, benzidine, 2,2'-bis-(trifluoromethyl) benzidine, tolylene diamine;
Described Amino End Group oligopolymer is Amino End Group polyamide oligomer, Amino End Group polyimide oligomer, Amino End Group polyester oligomer, amino-terminated polyurethane oligopolymer, Amino End Group polyureas oligopolymer, Amino End Group polycarbonate oligomer, Amino Terminated polyether(ATPE) sulfone oligopolymer, Amino End Group polyolefin oligomer, Amino End Group polyphenylene sulfide oligopolymer, Amino End Group polysiloxane oligomer, Amino Terminated polyether(ATPE) ketone oligopolymer, Amino Terminated polyether(ATPE) ketone oligopolymer, Amino End Group polyoxymethylene oligopolymer, Amino End Group polyaniline oligomer, Amino End Group linear phenolic resin oligopolymer, Amino End Group linear loop epoxy resins oligopolymer, Amino End Group polyolefin oligomer, Amino End Group polysiloxane oligomer, Amino Terminated polyether(ATPE) oligopolymer, Amino Terminated polyether(ATPE) ether ketone oligopolymer, one or more in Amino End Group polyaryletherketone oligopolymer.
8. according to the preparation method of the carbon dioxide-base polyureas of claim 1-3 described in any one, it is characterized in that, in described step one, when polyamine compounds is 1, 4-butanediamine, 1, 5-pentamethylene diamine, 2-methyl 1, 5-pentamethylene diamine, 1, 6-hexanediamine, 1, 7-heptamethylene diamine, 1, 8-octamethylenediamine, 1, 9-nonamethylene diamine, 1, 10-decamethylene diamine, 1, 11-11 methylene diamine, 1, 12-ten dimethylene diamines, 1, 13-ten trimethylene diamine, 1, 14-ten tetramethylene-diamine, 1, 15-ten five methylene diamine, 1, 16-ten hexamethylene-diamine, 1, 17-ten heptamethylene diamines or 1, during 18-18 methylene diamine, before step one purges carbonic acid gas in reaction unit, also in reaction unit, add diacid, one or more in dicarboxylic anhydride.
9. according to the preparation method of the carbon dioxide-base polyureas of claim 1-3 described in any one, it is characterized in that, in described step 2, before purging carbonic acid gas, also in reaction unit, add end-capping reagent and/or catalyzer, described end-capping reagent is unary primary amine, unitary secondary amine, monoprotic acid, unitary acid anhydrides, unitary acyl chlorides, unitary isocyanic ester, unitary epoxy compounds or ketone compounds; Described catalyzer is sodium hydroxide, magnesium hydroxide, cesium hydroxide, calcium oxide, magnesium oxide, zirconium white, metal carbonate, alkali metal bicarbonate salt, alkaline molecular sieve, alkaline exchange of particles resin, tertiary amine compounds, alkali ionic liquid, alkaline polymer sulfuric acid, hydrochloric acid, nitric acid, protonic acid, Lewis acid, aliphatic diacid or aromatic diacid.
10. the carbon dioxide-base polyureas prepared of the preparation method of the carbon dioxide-base polyureas of claim 1-3 described in any one, it is characterized in that, the number-average molecular weight of described carbon dioxide-base polyureas is 5000-50000.
The application of 11. carbon dioxide-base polyureas according to claim 10, it is characterized in that, by carbon dioxide-base polyureas and additive 100:(1-100 in mass ratio) blended, mixed by twin-screw extrusion or mechanical stirring, after dicing machine granulation, obtain the polyurea matrix resin of modification;
Described additive is one or more in softening agent, toughner, chemical stabilizer, coupling agent, antioxidant, photostabilizer, defoamer, mould inhibitor, static inhibitor, thinner, tinting material, dispersion agent, rheological agent, anti-sedimentation agent, weighting agent, whipping agent, acidifying preventing agent, fire retardant, flame retardant, thermo-stabilizer, fibrous supporting material, packing material, pigment.
The application of 12. carbon dioxide-base polyureas according to claim 10, it is characterized in that, by carbon dioxide-base polyureas and intermingling material 100:(1-100 in mass ratio) blended, mixed by twin-screw extrusion or mechanical stirring, after dicing machine granulation, obtain blending resin;
Described intermingling material is polyphenylene oxide, polyphenylene sulfide, polyester, polymeric amide, polycarbonate, poly(lactic acid), urethane, isocyanate-based polyureas, polyethersulfone, polyethylene, polypropylene, polystyrene, polypyrrole, Polythiophene, tetrafluoroethylene or polyvinyl chloride.
The application of 13. carbon dioxide-base polyureas according to claim 10, is characterized in that, by carbon dioxide-base polyureas through melt-spinning, solvent spinning or electrostatic spinning, obtain polyurea fiber.
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| CN105860059A (en) * | 2016-05-16 | 2016-08-17 | 中国科学院兰州化学物理研究所 | Method for preparing polyurea from CO2 and diamine in presence of ionic liquid catalyst |
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| CN111662447A (en) * | 2020-05-28 | 2020-09-15 | 天津大学 | Method for synthesizing porous functional ion polyurea material by solvothermal method |
| CN112011167A (en) * | 2020-09-08 | 2020-12-01 | 天津市昊航复合管业有限公司 | Polyurea elastomer anticorrosive material |
| CN115779791A (en) * | 2023-01-29 | 2023-03-14 | 山西拓扑力捷科技有限公司 | Method for preparing organic matter by continuous condensation reaction |
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