CN102718968B - Bio-based long-carbon-chain semi-alicyclic polyamide-imide PA10I and synthesizing method thereof - Google Patents
Bio-based long-carbon-chain semi-alicyclic polyamide-imide PA10I and synthesizing method thereof Download PDFInfo
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- 238000000034 method Methods 0.000 title abstract description 13
- 230000002194 synthesizing effect Effects 0.000 title abstract description 4
- 239000004962 Polyamide-imide Substances 0.000 title abstract 3
- 229920002312 polyamide-imide Polymers 0.000 title abstract 3
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 42
- -1 Maleopimaric acid acyl chloride Chemical class 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000000376 reactant Substances 0.000 claims abstract description 21
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- 125000002723 alicyclic group Chemical group 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- 239000011347 resin Substances 0.000 claims description 19
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- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 16
- 238000010189 synthetic method Methods 0.000 claims description 16
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- 239000012467 final product Substances 0.000 claims description 5
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- 235000019438 castor oil Nutrition 0.000 abstract 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 abstract 1
- 239000011261 inert gas Substances 0.000 abstract 1
- 239000003053 toxin Substances 0.000 abstract 1
- 231100000765 toxin Toxicity 0.000 abstract 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 abstract 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 11
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 11
- FEPCMSPFPMPWJK-OLPJDRRASA-N maleopimaric acid Chemical compound C([C@]12C=C([C@H](C[C@@H]11)[C@H]3C(OC(=O)[C@@H]23)=O)C(C)C)C[C@@H]2[C@]1(C)CCC[C@@]2(C)C(O)=O FEPCMSPFPMPWJK-OLPJDRRASA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- MHVJRKBZMUDEEV-APQLOABGSA-N (+)-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-APQLOABGSA-N 0.000 description 7
- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
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- 239000002253 acid Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
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- WBHHMMIMDMUBKC-QJWNTBNXSA-N ricinoleic acid Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(O)=O WBHHMMIMDMUBKC-QJWNTBNXSA-N 0.000 description 4
- 229960003656 ricinoleic acid Drugs 0.000 description 4
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
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- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a synthesizing method for bio-based long-carbon-chain semi- alicyclic polyimide-imide. Maleopimaric acid acyl chloride and 1,10-decamethylene diamine respectively made of gum rosin and castor oil as raw materials are put into a stirring-type polymerization reaction container; inert gases are fed after the stirring-type polymerization reaction container is vacuumized; the polymerization reaction container is heated hermetically; after the stirring speed of the polymerization reaction container is adjusted, the reactants are thermally insulated and pressurized, and the gases are discharged so as to obtain ordinary pressure; the polymerization reaction container is heated again, the stirring speed of the polymerization reaction container is adjusted, and the polymerization reaction container is continually vacuumized after constant temperature is obtained; and the bio-based long-carbon-chain semi-alicyclic polyimide is obtained after the reaction is over. The synthesizing method of the invention is based on the principle of melt polycondensation and the whole synthesis process does not require any organic solvent, so that no additional steps to recover organic solvent are needed , and no toxin or harm is generated to people and the environment. The synthesized polyamide-imide PA10I has the advantages of good heat resistance, high-temperature rigidity, dimensional stability and low water absorption. The polyamide-imide PA10I can be used for engineering plastics or film materials and the like.
Description
Technical field
The present invention relates to long carbochain half alicyclic polyamidoimide PA10I and the synthetic method thereof of a kind of bio-based.
Background technology
China is the big producing country of gum resin, and gum resin is the natural industrial chemicals of reproducibility, its contain the resinous acid of 90% left and right and 10% left and right ester and can not Saponification material.In resinous acid, main component is the abietic acid with conjugated double bond, and the conjugated double bond in the abietic acid molecular structure is not in same alicyclic ring, therefore can not carry out the Diels-Alder reaction with the double bond compound such as maleic anhydride, but at high temperature abietic acid reacts by isomerization equilibrium and can be converted into pimaric acid.And pimaric acid obtains maleopimaric anhydride by carrying out the Diels-Alder reaction with maleic anhydride.At last, maleopimaric anhydride obtains the maleopimaric acid acyl chlorides with the thionyl chloride reaction at normal temperatures.
China is the big producing country of Viscotrol C, and Viscotrol C is the natural industrial chemicals of reproducibility, and its main component is the ricinolic acid Witepsol W-S 55.The preparation process of 1，10-diaminodecane is as follows: Viscotrol C first obtains ricinolic acid through hydrolysis, and then alkaline splitting and acidifying obtain 1,10-sebacic acid, obtains 1，10-diaminodecane after last hydrogenation amination.
Polyamidoimide is to have important industry and a polymkeric substance of commercial value, in it is usually used in the fire-resistant fabric field or anti-height is hot injection member field.Contain simultaneously two kinds of modular constructions of acid amides and imide on the molecular backbone chain of polyamidoimide, thereby it has the resistance toheat of polyimide and the workability energy of polymeric amide, is a kind of high performance engineering plastics with good heat resistance, high temperature rigid, dimensional stability and low water absorption.The aromatic polyamide imide is the polymkeric substance with excellent mechanical property, but it is difficult to process by the approach of melting, and the half easier moulding of alicyclic polyamidoimide, it has the mobility excellent characteristics of aliphatic polyamide, and it has than the better mechanics of aliphatic polyamide and thermal property.
Usually the synthesis mechanism of polyamidoimide is solution polymerization, i.e. polymerization in the solution of organic solvent.Organic solvent in use has larger shortcoming, and on the one hand, after polymkeric substance is synthetic, its solvent recuperation needs additional step, and the recovery of the organic solvent that uses of the washing of the precipitation of polymkeric substance in poor solvent, polymkeric substance also needs additional step; On the other hand, some solvent is virose, therefore human body and environment is had danger.With the imido method of melt polymerization mechanism synthesizing polyamides, relevant report is not arranged at present.
Summary of the invention
Based on this, the invention provides the synthetic method of the long carbochain half alicyclic polyamidoimide PA10I of a kind of bio-based.
The synthetic method of the long carbochain half alicyclic polyamidoimide PA10I of a kind of bio-based comprises the following steps:
(1) take gum resin and Viscotrol C as raw material, prepare respectively maleopimaric acid acyl chlorides and 1，10-diaminodecane, drying;
(2) with dried maleopimaric acid acyl chlorides and 1,10-decamethylene diamine 1:0.85～1.15 in molar ratio adds in the stirring-type polymerization reactor, lead to rare gas element 1-30min after vacuumizing 1-30min, so circulate 1-20 time, the system pressure of controlling in polymerization reactor is 0.1-0.3MPa;
(3) be heated to 110-140 ℃ to polymerization reactor is airtight, after the stirring velocity of telo merization device was 0-500r/min, the pressure of controlling in polymerization reactor was 1.1-1.3MPa, to reactant heat-insulation pressure keeping 0.5-24 hour, exitted to normal pressure;
(4) again polymerization reactor is heated to 250-310 ℃, and after the stirring velocity of telo merization device is 0-200r/min, continues after constant temperature to vacuumize 1-24 hour, reaction finishes, and get final product.
Therein in some embodiment, described step (2) is: with the maleopimaric acid acyl chlorides and 1 after vacuum-drying, 10-decamethylene diamine 1:1.01～1.10 in molar ratio adds in the stirring-type polymerization reactor, lead to rare gas element 2-15min after vacuumizing 2-15min, so circulation is 4-8 time, and the system pressure of controlling in polymerization reactor is 0.1-0.3MPa.Before reaction, logical rare gas element purpose is to reduce the probability that side reaction occurs.
Therein in some embodiment, described step (3) is: be heated to 120-130 ℃ to polymerization reactor is airtight, after the stirring velocity of telo merization device is 100-300r/min, the pressure of controlling in polymerization reactor is 1.1-1.3MPa, to reactant heat-insulation pressure keeping 1-3 hour, exit to normal pressure.
In some embodiment, described step (4) is therein: again polymerization reactor is heated to 270-300 ℃, and after the stirring velocity of telo merization device is 25-100r/min, continues after constant temperature to vacuumize 3-10 hour, reaction finishes, and get final product.The purpose that vacuumizes in reaction process is that the water that produces in polycondensation is removed, and is conducive to the polyreaction forward and carries out.
In embodiment, described rare gas element is nitrogen therein.
The present invention is as follows by the reaction equation of maleopimaric acid acyl chlorides and the long carbochain half alicyclic polyamidoimide PA10I of 1，10-diaminodecane synthesising biological base:
The structural formula of the long carbochain half alicyclic polyamidoimide PA10I of the bio-based for preparing is as follows:
Wherein, n=1-200.The melt temperature of PA10I is between 250-270 ℃.
The preparation technology of the long carbochain half alicyclic polyamidoimide PA10I of bio-based of the present invention has the following advantages:
1. the method for the long carbochain half alicyclic polyamidoimide PA10I of synthesising biological base of the present invention is based on the principle of melt polymerization, whole building-up process does not need to use any organic solvent, therefore, do not need additional step to reclaim organic solvent, and to human body and environment toxicological harmless;
2. synthesising biological base of the present invention is grown the method simple process of carbochain half alicyclic polyamidoimide PA10I, and polymerization process is easy to operate, is convenient to management and control, can reach fully desired polymerizing condition, facilitates its industrialized realization;
3. the raw material Viscotrol C and the gum resin that use of the method for the long carbochain half alicyclic polyamidoimide PA10I of synthesising biological base of the present invention is easy to get, and all belongs to renewable resources, and the polyamidoimide PA10I that is synthesized by them belongs to biomaterial completely; The long carbochain half alicyclic polyamidoimide of the bio-based for preparing has good heat resistance, high temperature rigid, dimensional stability and low water absorption, can be used for the heat-resistant part of mechanical field, electrical/electronic field, automotive field and aerospace field or as mould material.
Embodiment
Describe the present invention in detail below in conjunction with specific embodiment.
In following examples, be by gum resin and Viscotrol C that raw material prepares the method for maleopimaric acid acyl chlorides and 1，10-diaminodecane respectively as follows:
(1) preparation of maleopimaric acid acyl chlorides
Gum resin is the natural industrial chemicals of reproducibility, its contain the resinous acid of 90% left and right and 10% left and right ester and can not Saponification material.In resinous acid, main component is the abietic acid with conjugated double bond, and the conjugated double bond in the abietic acid molecular structure is not in same alicyclic ring, therefore can not carry out the Diels-Alder reaction with the double bond compound such as maleic anhydride, but at high temperature abietic acid reacts by isomerization equilibrium and can be converted into pimaric acid.Pimaric acid obtains maleopimaric anhydride by carrying out the Diels-Alder reaction with maleic anhydride.At last, maleopimaric anhydride obtains the maleopimaric acid acyl chlorides with the thionyl chloride reaction at normal temperatures.
Gum resin is available from Guangzhou green bright and beautiful resin company limited.
1. the gum resin abietic acid of purifying out:
Add 210 weight part gasoline (boiling range is 90-100 ℃) and 100 weight part gum resin in the four-hole bottle that mechanical stirring, prolong and thermometer are housed, the stirring velocity of starting agitator is 50r/min, and low-grade fever to 40 ℃, makes gum resin dissolving clarification.Slowly add 30 weight part hexahydroaniline to be dissolved in the solution of 35 weight part gasoline (specification is the same), form a large amount of white precipitates, after 40 ℃ of insulation reaction 1h, be cooled to below 5 ℃ and keep 30min with ice-water bath, vacuum filtration passes through the cooling gasoline washing precipitation of ice-water baths 3 times with 18 weight parts.After 40 ℃ of vacuum drying oven inner dryings, grind into powder also is placed in the there-necked flask that mechanical stirring, prolong is housed and is added with 55 weight part ether, the stirring velocity of starting agitator is 50r/min, white powder is suspended in ether, drip hydrochloric acid soln that concentration is 2mol/L under room temperature in the flask until the white powder completely dissolve after continuing to stir 30min, is transferred to mixture in separating funnel, remove water layer and use the distilled water repetitive scrubbing, until aqueous pH values is 6.The most of ether in organic phase is removed in air distillation, and strong solution is transferred in watch-glass, obtains abietic acid after 40 ℃ of vacuum-dryings.
2. the abietic acid isomerization prepares pimaric acid:
Add abietic acid in the there-necked flask that mechanical stirring, thermometer are housed, logical nitrogen 15min is present in environment under nitrogen protection reactant.Be heated to 180 ℃, and after the stirring velocity of regulating agitator was 50r/min, then thermostatically heating 2 hours was cooled to room temperature, obtains the pimaric acid that yellow is solidified the shape crystal.
The reaction equation that the abietic acid isomerization prepares pimaric acid is as follows:
3. the preparation of maleopimaric anhydride:
Add 100 weight part pimaric acids, 17 weight part maleic anhydrides, 3.33 weight part p-methyl benzenesulfonic acids (TSA), 55 weight part Glacial acetic acid in the four-hole bottle that mechanical stirring, water trap, prolong and thermometer are housed after; logical nitrogen 15min is present in environment under nitrogen protection reactant.Slowly be heated to 110 ℃, after material melts substantially, the stirring velocity of turn on agitator is 50r/min, and continue evenly to heat up, regulate a bottle interior reaction temperature by the acetic acid amount in the conditioned reaction bottle, after in the question response bottle, temperature rises to 180 ℃, kept this temperature 4 hours, cooling adds 210 weight part Glacial acetic acid, and stirs evenly after temperature in reaction flask is down to 110 ℃.When material is down to room temperature, further use frozen water cooling, obtain maleopimaric anhydride white crystals crude product through suction filtration.The maleopimaric anhydride crude product is washed through sherwood oil after using the Glacial acetic acid recrystallization, in 60 ℃ of vacuum-dryings, obtains the maleopimaric anhydride white, needle-shaped crystals.
The chemical equation of maleopimaric anhydride preparation:
4. the preparation of maleopimaric acid acyl chlorides:
In the there-necked flask that mechanical stirring and thermometer are housed, add the maleopimaric anhydride of 100 weight parts, logical nitrogen 15min is present in environment under nitrogen protection reactant.100 weight parts are newly steamed thionyl chloride dropwise to be joined in flask with constant pressure funnel, the stirring velocity of turn on agitator is 25r/min, and use water-bath to control the flask interior reaction temperature at 25 ℃, kept this temperature 48 hours, excessive thionyl chloride is revolved with Rotary Evaporators be steamed out, separate out a large amount of crystal at bottle wall or fluid surface, the crystal that obtains first washs with ether, recrystallization 3 times from benzene again, obtaining crystalline material is the maleopimaric acid acyl chlorides.
The chemical equation of maleopimaric acid acyl chlorides preparation:
(2) preparation of 1，10-diaminodecane
Viscotrol C is the natural industrial chemicals of reproducibility, and its main component is the ricinolic acid Witepsol W-S 55.The preparation process of 1，10-diaminodecane is as follows: Viscotrol C first obtains ricinolic acid through hydrolysis, and then alkaline splitting and acidifying obtain 1,10-sebacic acid, obtains 1，10-diaminodecane after last hydrogenation amination.
1，10-diaminodecane used in the embodiment of the present invention is available from Suzhou Hanpu Polymer Material Co., Ltd..
The reaction equation of the long carbochain half alicyclic polyamidoimide PA10I of synthesising biological base of the present invention is as follows:
Wherein, n=1-200.
The synthetic method of the long carbochain half alicyclic polyamidoimide PA10I of 1 one kinds of bio-based of embodiment
Comprise the following steps:
(1) take gum resin and Viscotrol C as raw material, prepare respectively maleopimaric acid acyl chlorides and 1，10-diaminodecane, vacuum-drying;
(2) with dried maleopimaric acid acyl chlorides and 1, the 10-decamethylene diamine adds in the stirring-type polymerization reactor for 4.190kg:1.462kg (mol ratio 1:0.85) in mass ratio, vacuumize helium injection gas 30min after 1min, so circulation is 20 times, reactant is present in environment under nitrogen protection, controls that in reactor, system pressure is 0.3MPa;
(3) be heated to 110 ℃ to reactor is airtight, control that in reactor, system pressure is 1.1MPa, to reactant heat-insulation pressure keeping 24 hours, slowly exit to normal pressure;
(4) reheat 250 ℃, continue after constant temperature to vacuumize 24 hours, reaction finishes.Fill the helium discharging,, pelletizing cooling through tank prepares PA10I.
The synthetic method of the long carbochain half alicyclic polyamidoimide PA10I of 2 one kinds of bio-based of embodiment
Comprise the following steps:
(1) take gum resin and Viscotrol C as raw material, prepare respectively maleopimaric acid acyl chlorides and 1，10-diaminodecane, vacuum-drying;
(2) with dried maleopimaric acid acyl chlorides and 1, the 10-decamethylene diamine adds in the stirring-type polymerization reactor for 4.190kg:1.634kg (mol ratio 1:0.95) in mass ratio, lead to nitrogen 1min after vacuumizing 30min, so circulation is 1 time, reactant is present in environment under nitrogen protection, controls that in reactor, system pressure is 0.1MPa;
(3) be heated to 140 ℃ to reactor is airtight, and after the stirring velocity of telo merization device is 500r/min, control that in reactor, system pressure is 1.3MPa, to reactant heat-insulation pressure keeping 0.5 hour, slowly exit to normal pressure;
(4) reheat 310 ℃, and after the stirring velocity of telo merization device is 200r/min, continue after constant temperature to vacuumize 1 hour, reaction finishes.The inflated with nitrogen discharging,, pelletizing cooling through tank prepares PA10I.
The synthetic method of the long carbochain half alicyclic polyamidoimide PA10I of 3 one kinds of bio-based of embodiment
Comprise the following steps:
(1) take gum resin and Viscotrol C as raw material, prepare respectively maleopimaric acid acyl chlorides and 1，10-diaminodecane, vacuum-drying;
(2) with dried maleopimaric acid acyl chlorides and 1, the 10-decamethylene diamine adds in the stirring-type polymerization reactor for 4.190kg:1.720kg (mol ratio 1:1) in mass ratio, lead to nitrogen 2min after vacuumizing 10min, so circulation is 6 times, reactant is present in environment under nitrogen protection, controls that in reactor, system pressure is 0.2MPa;
(3) be heated to 130 ℃ to reactor is airtight, and after the stirring velocity of telo merization device is 200r/min, control that in reactor, system pressure is 1.2MPa, to reactant heat-insulation pressure keeping 1 hour, slowly exit to normal pressure;
(4) reheat 280 ℃, and after the stirring velocity of telo merization device is 50r/min, continue after constant temperature to vacuumize 8 hours, reaction finishes.The inflated with nitrogen discharging,, pelletizing cooling through tank prepares PA10I.
The synthetic method of the long carbochain half alicyclic polyamidoimide PA10I of 4 one kinds of bio-based of embodiment
Comprise the following steps:
(1) take gum resin and Viscotrol C as raw material, prepare respectively maleopimaric acid acyl chlorides and 1，10-diaminodecane, vacuum-drying;
(2) with dried maleopimaric acid acyl chlorides and 1, the 10-decamethylene diamine adds in the stirring-type polymerization reactor for 4.190kg:1.806kg (mol ratio 1:1.05) in mass ratio, lead to nitrogen 2min after vacuumizing 10min, so circulation is 6 times, reactant is present in environment under nitrogen protection, controls that in reactor, system pressure is 0.2MPa;
(3) be heated to 130 ℃ to reactor is airtight, and after the stirring velocity of telo merization device is 200r/min, control that in reactor, system pressure is 1.2MPa, to reactant heat-insulation pressure keeping 2 hours, slowly exit to normal pressure;
(4) reheat 280 ℃, and after the stirring velocity of telo merization device is 50r/min, continue after constant temperature to vacuumize 8 hours, reaction finishes.The inflated with nitrogen discharging,, pelletizing cooling through tank prepares PA10I.
The synthetic method of the long carbochain half alicyclic polyamidoimide PA10I of 5 one kinds of bio-based of embodiment
Comprise the following steps:
(1) take gum resin and Viscotrol C as raw material, prepare respectively maleopimaric acid acyl chlorides and 1，10-diaminodecane, vacuum-drying;
(2) with dried maleopimaric acid acyl chlorides and 1, the 10-decamethylene diamine adds in the stirring-type polymerization reactor for 4.190kg:1.892kg (mol ratio 1:1.1) in mass ratio, lead to nitrogen 2min after vacuumizing 10min, so circulation is 6 times, reactant is present in environment under nitrogen protection, controls that in reactor, system pressure is 0.2MPa;
(3) be heated to 130 ℃ to reactor is airtight, and after the stirring velocity of telo merization device is 200r/min, control that in reactor, system pressure is 1.2MPa, to reactant heat-insulation pressure keeping 2 hours, slowly exit to normal pressure;
(4) reheat 290 ℃, and after the stirring velocity of telo merization device is 50r/min, continue after constant temperature to vacuumize 6 hours, reaction finishes.The inflated with nitrogen discharging,, pelletizing cooling through tank prepares PA10I.
The synthetic method of the long carbochain half alicyclic polyamidoimide PA10I of 6 one kinds of bio-based of embodiment
Comprise the following steps:
(1) take gum resin and Viscotrol C as raw material, prepare respectively maleopimaric acid acyl chlorides and 1，10-diaminodecane, vacuum-drying;
(2) with dried maleopimaric acid acyl chlorides and 1, the 10-decamethylene diamine adds in the stirring-type polymerization reactor for 4.190kg:1.978kg (mol ratio 1:1.15) in mass ratio, lead to nitrogen 2min after vacuumizing 10min, so circulation is 6 times, reactant is present in environment under nitrogen protection, controls that in reactor, system pressure is 0.2MPa;
(3) be heated to 130 ℃ to reactor is airtight, and after the stirring velocity of telo merization device is 200r/min, control that in reactor, system pressure is 1.3MPa, to reactant heat-insulation pressure keeping 1 hour, slowly exit to normal pressure;
(4) reheat 300 ℃, and after the stirring velocity of telo merization device is 50r/min, continue after constant temperature to vacuumize 6 hours, reaction finishes.The inflated with nitrogen discharging,, pelletizing cooling through tank prepares PA10I.
The preparation-obtained PA10I of embodiment 1-6 is carried out following performance test:
1. number-average molecular weight: by the gel permeation chromatography in methylene dichloride and trifluoroacetic anhydride mixed solvent, then absorb by differential refraction method, UV and the triplicate of viscosimetric analysis is measured the number-average molecular weight of polymkeric substance.
2. melt temperature: press the ASTM-D3418 standard testing;
3. tensile property: press the ASTM-D638 standard testing, rate of extension 50mm/min;
4. impact property: press the ASTM-D256 standard testing, batten thickness is 3.2mm, 23 ℃, and 50%RH;
5. bending property: press the ASTM-D790 standard testing, crooked speed 10mm/min;
6. water-intake rate: press the ASTM-D570 standard testing;
7. shrinking percentage: press the ISO294-4 standard testing;
8. heat-drawn wire: press the ASTM-D648 standard testing, batten thickness is 6.4mm.
The physicals of the PA10I that embodiment 1-6 prepares is as shown in table 1:
The physicals of the PA10I that table 1 embodiment 1-6 prepares
As can be seen from the above table, the over-all properties of the polyamidoimide PA10I that embodiment 4 and 5 prepares will be got well compared to the over-all properties of the polyamidoimide PA10I that other embodiment prepare, and the over-all properties of the polyamidoimide PA10I that embodiment 4 prepares is best.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.Should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (6)
1. the synthetic method of the long carbochain half alicyclic polyamidoimide PA10I of bio-based, is characterized in that, comprises the following steps:
(1) take gum resin and Viscotrol C as raw material, prepare respectively maleopimaric acid acyl chlorides and 1，10-diaminodecane, drying;
(2) with dried maleopimaric acid acyl chlorides and 1,10-decamethylene diamine 1:0.85～1.15 in molar ratio adds in the stirring-type polymerization reactor, lead to rare gas element 1-30min after vacuumizing 1-30min, so circulate 1-20 time, the system pressure of controlling in polymerization reactor is 0.1-0.3MPa;
(3) be heated to 110-140 ℃ to polymerization reactor is airtight, after the stirring velocity of telo merization device was 0-500r/min, the pressure of controlling in polymerization reactor was 1.1-1.3MPa, to reactant heat-insulation pressure keeping 0.5-24 hour, exitted to normal pressure;
(4) again polymerization reactor is heated to 250-310 ℃, and after the stirring velocity of telo merization device is 0-200r/min, continues after constant temperature to vacuumize 1-24 hour, reaction finishes, and get final product.
2. bio-based according to claim 1 is grown the synthetic method of carbochain half alicyclic polyamidoimide PA10I, it is characterized in that, described step (2) is: with the maleopimaric acid acyl chlorides and 1 after vacuum-drying, 10-decamethylene diamine 1:1.01～1.10 in molar ratio adds in the stirring-type polymerization reactor, lead to rare gas element 2-15min after vacuumizing 2-15min, so circulation is 4-8 time, and the system pressure of controlling in polymerization reactor is 0.1-0.3MPa.
3. bio-based according to claim 1 is grown the synthetic method of carbochain half alicyclic polyamidoimide PA10I, it is characterized in that, described step (3) is: be heated to 120-130 ℃ to polymerization reactor is airtight, after the stirring velocity of telo merization device is 100-300r/min, the pressure of controlling in polymerization reactor is 1.1-1.3MPa, to reactant heat-insulation pressure keeping 1-3 hour, exit to normal pressure.
4. bio-based according to claim 1 is grown the synthetic method of carbochain half alicyclic polyamidoimide PA10I, it is characterized in that, described step (4) is: again polymerization reactor is heated to 270-300 ℃, and after the stirring velocity of telo merization device is 25-100r/min, continue after constant temperature to vacuumize 3-10 hour, reaction finishes, and get final product.
5. the synthetic method of according to claim 1-4 long carbochain half alicyclic polyamidoimide PA10I of the described bio-based of any one, is characterized in that, described rare gas element is nitrogen.
6. the synthetic method of the long carbochain half alicyclic polyamidoimide PA10I of bio-based according to claim 5, is characterized in that, comprises the following steps:
(1) take gum resin and Viscotrol C as raw material, prepare respectively maleopimaric acid acyl chlorides and 1，10-diaminodecane, drying;
(2) with the maleopimaric acid acyl chlorides and 1 after vacuum-drying, 10-decamethylene diamine 1:1.01～1.10 in molar ratio adds in the stirring-type polymerization reactor, lead to nitrogen 2-15min after vacuumizing 2-15min, so circulate 4-8 time, the system pressure of controlling in polymerization reactor is 0.1-0.3MPa;
(3) be heated to 120-130 ℃ to polymerization reactor is airtight, after the stirring velocity of telo merization device was 100-300r/min, the pressure of controlling in polymerization reactor was 1.1-1.3MPa, to reactant heat-insulation pressure keeping 1-3 hour, exitted to normal pressure;
(4) again polymerization reactor is heated to 270-300 ℃, and after the stirring velocity of telo merization device is 25-100r/min, continues after constant temperature to vacuumize 3-10 hour, reaction finishes, and get final product.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3503998A (en) * | 1968-11-13 | 1970-03-31 | Us Agriculture | Reaction products of diamines and the monoacid chloride of maleopimaric acid |
| US3522211A (en) * | 1966-12-02 | 1970-07-28 | Us Agriculture | Polyimide-polyamides from maleopimaric acid derivatives |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3522211A (en) * | 1966-12-02 | 1970-07-28 | Us Agriculture | Polyimide-polyamides from maleopimaric acid derivatives |
| US3503998A (en) * | 1968-11-13 | 1970-03-31 | Us Agriculture | Reaction products of diamines and the monoacid chloride of maleopimaric acid |
Non-Patent Citations (3)
| Title |
|---|
| 李春成等.脂松香合成聚酰胺酰亚胺研究进展.《塑料工业》.1996,(第5期), |
| 脂松香合成聚酰胺酰亚胺研究进展;李春成等;《塑料工业》;19961231(第5期);第94-96页 * |
| 脂松香合成聚酰胺酰亚胺研究进展;李春成等;《塑料工业》;19961231(第5期);第94页 * |
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