CN1098875C - Process for synthesizing dimer acid type polyamide resin - Google Patents
Process for synthesizing dimer acid type polyamide resin Download PDFInfo
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- CN1098875C CN1098875C CN00100075A CN00100075A CN1098875C CN 1098875 C CN1098875 C CN 1098875C CN 00100075 A CN00100075 A CN 00100075A CN 00100075 A CN00100075 A CN 00100075A CN 1098875 C CN1098875 C CN 1098875C
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Abstract
The present invention provides a synthesis method for dimeric acid type polyamide resin. The defect that the initial volume of a reaction system is difficult to control in the prior art is solved by the method that a proper amount of organic inert solvent is added into the reaction system during a reactive initial stage. The stable reactive state of the reaction system is kept during an initial period, and an agglomeration phenomenon which possibly occurs in the reaction system is prevented.
Description
The present invention relates to a kind of synthetic method of hot melt adhesive, specifically, the present invention relates to a kind of synthetic method of dimer acid type polyamide resin.
Polyamide resin is a kind of application hot melt adhesive very widely, particularly dimer acid type polyamide resin, with its excellent comprehensive performance, is widely used in fields such as hot melt adhesive, printing ink, coating.The synthetic method of dimer acid type polyamide resin also has a variety of, if polymeric amide is made by diprotic acid, then its chemical structural formula can be represented with following general formula:
If with hexanolactam open loop or other lactan open loops, then its chemical structural formula can be represented with following general formula:
U.S. Pat 3377303 and US4853460 all disclose the synthetic method of relevant dimer acid type polyamide resin, and this method comprises the steps:
(1) will react starting raw material and add reactor, under nitrogen protection, stir.
(2) reactor heating is to 130-160 ℃, and the fractionation by distillation water that goes out to generate.
(3) progressively heating kept 3-4 hour under 200-300 ℃ of condition, wherein reacted under vacuum or decompression state in last 1-2 hour, and the pressure of reaction is 0.5-25mmHg.
(4) discharging.
When the method that adopts above-mentioned patent is carried out diprotic acid polymerization synthesis of dimmer acid type polyamide resin, owing to produce a large amount of tiny and stable bubbles, the volume of reaction system is acutely risen greatly in initial reaction stage, make reaction be difficult to control; In addition, the system volume rises too fastly greatly in the reaction process, makes the stirring of material and dispersiveness all be difficult for grasping, and occurs the phenomenon of caking in the system easily, has finally influenced the performance of polyamide resin.
The objective of the invention is to problem at above-mentioned prior art existence, a kind of synthetic method of dimer acid type polyamide resin is provided, method of the present invention has been avoided the uppity shortcoming of volume at reaction system initial stage in the prior art, makes the reaction system initial stage keep stable response behaviour.
To describe technical scheme of the present invention in detail below.
The synthetic method of polyamide resin of the present invention, its key are to add an amount of organic inert solvent at the initial period of reaction in reaction system.
Organic inert solvent of the present invention should satisfy following condition:
(1) in reaction process, do not participate in the polycondensation of polymeric amide, in polycondensation, do not carry out side reaction yet.
(2) boiling point of organic inert solvent is between 50-130 ℃, and preferred boiling spread is 60-120 ℃.
(3) consumption of organic inert solvent accounts for the 1-10% of reaction raw materials gross weight, and preferred amount ranges is 3-6%.
Organic inert solvent of the present invention is alkane, aromatic hydrocarbons, ester, ketone or their mixture.
Wherein said alkane is selected from methane, ethane, propane, butane, Skellysolve A, iso-pentane, neopentane, normal hexane, isohexane, hexanaphthene, 3-methylpentane, normal heptane, octane, octane-iso.
Described aromatic hydrocarbons is selected from benzene, toluene, ethylbenzene.
Described ester is selected from methyl-formiate, methyl acetate, ethyl acetate, butylacetate, isobutyl acetate, ethyl butyrate, methyl methacrylate.
Described ketone is selected from acetone, butanone, pentanone-2, pentanone-3,4-methyl-2-pentanone-2.
The synthetic method of dimer acid type polyamide resin of the present invention comprises the steps:
(1) will react starting raw material and described organic inert solvent adding reactor, stir and logical nitrogen protection;
(2) reactor heating is to 120-160 ℃, and water and organic inert solvent of generation are told in distillation;
(3) progressively heating makes temperature of reaction surpass 200 ℃, keeps 3-4 hour between 200-300 ℃ in temperature of reaction; Wherein last 1-2 hour of reaction is to react under the 0.5-25mmHg in reaction pressure;
(4) discharging.
The synthetic method of dimer acid type polyamide resin of the present invention has following beneficial effect:
1. the present invention adopts the method for the organic inert solvent of adding to destroy the last structure of a large amount of tiny and stable bubble that exists in the prior art reaction system, make organic inert solvent in reaction system to seethe with excitement fast than the mode at bulla end, thereby avoided acutely rising of initial reaction stage reaction system volume big, made stable the carrying out of polycondensation process of initial reaction stage.
2. because the violent boiling in reaction system of organic inert solvent, help the homodisperse of each reactant in the reaction system, prevented the caking phenomenon that may occur in the reaction system.
3. in the actual production of prior art, each manufacturer often comes acutely rising of initial reaction stage system volume controlled greatly by the way that prolongs the reaction times, adopt method of the present invention to react, the reaction times of initial reaction stage is shortened greatly, improved the combined coefficient of resin.
Describe the present invention further below by embodiment, the present invention is more in depth understood with promotion.But the present invention is not subjected to the restriction of these embodiment.Those skilled in the art can make amendment or improve under the guide of spirit of the present invention the present invention, all belong to apparent.Propose in protection scope of the present invention appended claims book below.
Embodiment
Embodiment 1
With 150g (0.522mol) dimeracid, 8.5g hexanodioic acid, 14.6g quadrol, 7.0g being 81.4 ℃ hexanaphthene adding, piperazine, 5.4g boiling point have condensing reflux, stir, in the there-necked flask of logical nitrogen, heating and logical nitrogen are up to 120 ℃, system begins to rise greatly, reduce heating, hexane comes to life and refluxes in the system, the system stable reaction, strengthen heating, tell the portion water that hexane and reaction produce in 2-3 hour, system temperature progressively reaches 220-240 ℃, under this temperature, reacted 3 hours, wherein last 2 hours is to carry out under the 10mmHg at pressure, and discharging obtains softening temperature and be 153 ℃ yellow PA resin.
Embodiment 2
With 150g (0.522mol) dimeracid, 8.5g hexanodioic acid, 14.6g quadrol, 7.0g being 81.4 ℃ hexanaphthene adding, piperazine, 10.8g boiling point have condensing reflux, stir, in the there-necked flask of logical nitrogen, heating and logical nitrogen are up to 120 ℃, system begins to rise greatly, reduce heating, hexane comes to life and refluxes in the system, the system stable reaction, strengthen heating, tell the portion water that hexane and reaction produce in 2-3 hour, system temperature progressively reaches 220-240 ℃, under this temperature, reacted 3 hours, wherein last 2 hours is to carry out under the 10mmHg at pressure, and discharging obtains softening temperature and be 151 ℃ yellow PA resin.
Embodiment 3
With 150g (0.522mol) dimeracid, 8.5g hexanodioic acid, 14.6g being 81.4 ℃ hexanaphthene adding, quadrol, 7.0g piperazine, 18.0g boiling point have condensing reflux, stir, in the there-necked flask of logical nitrogen, heating and logical nitrogen are up to about 110 ℃, hexane is many in the system, and also begin to rise greatly boiling morning, reduces heating, hexane comes to life and refluxes in the system, the system stable reaction strengthens heating, tells the portion water that hexane and reaction produce in 2-3 hour, system temperature progressively reaches 220-240 ℃, under this temperature, reacted 3 hours, wherein last 2 hours is to carry out under the 10mmHg at pressure, discharging obtains softening temperature and is 148 ℃ yellow PA resin.
Embodiment 4
With 2300g (8.0mol) dimeracid, the 65g hexanodioic acid, the 90g sebacic acid, 197.5g quadrol, 141.5g piperazine, the 48g boiling point is that 81.4 ℃ hexanaphthene adding has condensing reflux, stir, in the there-necked flask of logical nitrogen, heating and logical nitrogen are up to about 125 ℃, and system begins to rise greatly, reduce heating, hexane comes to life and refluxes in the system, the system stable reaction strengthens heating, tells the portion water that hexane and reaction produce in 2-3 hour, system temperature progressively reaches 220-240 ℃, under this temperature, reacted 3 hours, wherein last 2 hours is to carry out under the 10mmHg at pressure, discharging obtains softening temperature and is 128 ℃ yellow PA resin.
Embodiment 5
With 100g (0.32mol) dimeracid, 5.8g hexanodioic acid, 6.6g quadrol, 9.5g piperazine, 5.0g being 80.0 ℃ benzene adding, boiling point has condensing reflux, stir, in the there-necked flask of logical nitrogen, heating and logical nitrogen are up to 120 ℃, and system begins to rise greatly, reduce heating, benzene comes to life in the system, appearance is than macrofoam, and backflow, the system stable reaction, strengthen heating, tell the portion water that benzene and reaction produce in 2-3 hour, system temperature progressively reaches 220-240 ℃, under this temperature, reacted 3 hours, wherein last 2 hours is to carry out under the 10mmHg at pressure, and discharging obtains softening temperature and be 131 ℃ yellow PA resin.
Embodiment 6
With 150g (0.522mol) dimeracid, 8.5g hexanodioic acid, 14.6g being 110.6 ℃ toluene adding, quadrol, 7.0g piperazine, 3.2g boiling point have condensing reflux, stir, in the there-necked flask of logical nitrogen, heating and logical nitrogen are up to 130 ℃, system begins to rise greatly, reduces heating, and toluene comes to life in the system, play macrofoam, and reflux, the system stable reaction strengthens heating, tell the portion water that toluene and reaction produce in 2-3 hour, system temperature progressively reaches 220-240 ℃, and reaction is 3 hours under this temperature, and wherein last 2 hours is to carry out under the 10mmHg at pressure, discharging obtains softening temperature and is 152 ℃ yellow PA resin.
Embodiment 7
With 150g (0.522mol) dimeracid, 8.5g hexanodioic acid, 14.6g quadrol, 7.0g piperazine, 7.2g boiling point are 117 ℃ 4-methyl-2-pentanone-2, the hexanaphthene of 4.0g (2.2wt%) adds and has condensing reflux, stir, in the there-necked flask of logical nitrogen, heating and logical nitrogen are up to 120 ℃, system begins to rise greatly, reduces heating, hexane in the system, butanone comes to life and refluxes, the system stable reaction, strengthen heating, tell hexane in 2-3 hour, the portion water that butanone and reaction produce, system temperature progressively reaches 220-240 ℃, reaction is 3 hours under this temperature, wherein last 2 hours is to carry out under the 10mmHg at pressure, discharging, the yellow PA resin that obtains.
Embodiment 8
With 150g (0.522mol) dimeracid, 8.5g hexanodioic acid, 14.6g being 126.5 ℃ butylacetate adding, quadrol, 7.0g piperazine, 7.2g boiling point have condensing reflux, stir, in the there-necked flask of logical nitrogen, heating and logical nitrogen are up to 130 ℃, system begins to rise greatly, reduces heating, and toluene comes to life in the system, play macrofoam, and reflux, the system stable reaction strengthens heating, tell the portion water that ethyl acetate and reaction produce in 2-3 hour, system temperature progressively reaches 220-240 ℃, and reaction is 3 hours under this temperature, and wherein last 2 hours is to carry out under the 10mmHg at pressure, discharging obtains softening temperature and is 149 ℃ yellow PA resin.
Embodiment 9
With 150g (0.522mol) dimeracid, 8.5g hexanodioic acid, 14.6g quadrol, 7.0g being 69.0 ℃ hexane adding, piperazine, 10.8g boiling point have condensing reflux, stir, in the there-necked flask of logical nitrogen, heating and logical nitrogen are up to 120 ℃, system begins to rise greatly, reduce heating, hexane comes to life and refluxes in the system, the system stable reaction, strengthen heating, tell the portion water that hexane and reaction produce in 2-3 hour, system temperature progressively reaches 220-240 ℃, under this temperature, reacted 3 hours, wherein last 2 hours is to carry out under the 10mmHg at pressure, and discharging obtains softening temperature and be 151 ℃ yellow PA resin.
Comparative example 1
With 150g (0.522mol) dimeracid, 8.5g hexanodioic acid, 14.6g quadrol, 7.0g adding, piperazine has condensing reflux, stir, in the there-necked flask of logical nitrogen, heating and logical nitrogen are up to 130-140 ℃, and system begins to produce fine and close tiny foam, and it is big to rise, and reduces heating, and system continues to rise greatly, and go out reactor, cooling reactor, system falls after rise, a little heat, system rises again greatly fast, react wayward, because foam is fine and close tiny, system is difficult to stir fully, generated a spot of light yellow block, reduce heating, the control heating, it is big too many that system is not risen, reacted 2-3 hour, after system appearance backflow, strengthen heating, tell hexane and the portion water of reacting generation in 1-2 hour, system temperature progressively reaches 220-240 ℃, reaction is 3 hours under this temperature, and wherein last 2 hours is to carry out discharging under the 10mmHg at pressure, obtaining softening temperature is about 152 ℃ yellow PA resin, can find in the resin that a spot of caking thing exists.
Claims (7)
1. the synthetic method of a dimer acid type polyamide resin is characterized in that, described method comprises the steps:
(1) will react starting raw material and organic inert solvent and add reactor, stir and logical nitrogen protection;
(2) reactor heating is to 120-160 ℃, and water and organic inert solvent of generation are told in distillation;
(3) progressively heating makes temperature of reaction surpass 200 ℃, keeps 3-4 hour between 200-300 ℃ in temperature of reaction; Wherein last 1-2 hour of reaction is to react under the 0.5-25mmHg in reaction pressure;
(4) discharging;
Wherein said starting raw material comprises dimeracid, hexanodioic acid, quadrol, piperazine; Described organic inert solvent is alkane, aromatic hydrocarbons, ester, ketone or their mixture, and its consumption is the 1-10% of reaction raw materials gross weight; The boiling spread of described organic inert solvent is 50-130 ℃.
2. synthetic method according to claim 1 is characterized in that, the consumption of described organic inert solvent is the 3-6% of reaction raw materials gross weight.
3. synthetic method according to claim 1, it is characterized in that described alkane is a kind of in methane, ethane, propane, butane, Skellysolve A, iso-pentane, neopentane, normal hexane, isohexane, hexanaphthene, 3-methylpentane, normal heptane, octane, the octane-iso or their mixture.
4. synthetic method according to claim 1 is characterized in that, described aromatic hydrocarbons is a kind of in benzene, toluene, the ethylbenzene or their mixture.
5. synthetic method according to claim 1 is characterized in that, described ester is a kind of in methyl-formiate, methyl acetate, ethyl acetate, butylacetate, isobutyl acetate, ethyl butyrate, the methyl methacrylate or their mixture.
6. synthetic method according to claim 1 is characterized in that, described ketone is a kind of in acetone, butanone, pentanone-2, pentanone-3, the 4-methyl-2-pentanone-2 or their mixture.
7. synthetic method according to claim 1 is characterized in that, the boiling spread of described organic inert solvent is 60-120 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00100075A CN1098875C (en) | 2000-01-05 | 2000-01-05 | Process for synthesizing dimer acid type polyamide resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00100075A CN1098875C (en) | 2000-01-05 | 2000-01-05 | Process for synthesizing dimer acid type polyamide resin |
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| Publication Number | Publication Date |
|---|---|
| CN1302826A CN1302826A (en) | 2001-07-11 |
| CN1098875C true CN1098875C (en) | 2003-01-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN00100075A Expired - Fee Related CN1098875C (en) | 2000-01-05 | 2000-01-05 | Process for synthesizing dimer acid type polyamide resin |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100580008C (en) * | 2007-09-10 | 2010-01-13 | 南京工业大学 | Waterborne dimer acid amide curing agent, preparation method and application thereof |
| CN102492135A (en) * | 2011-11-30 | 2012-06-13 | 上海天洋热熔胶有限公司 | Method for synthesizing dimer acid type polyamide hot melt adhesive |
| CN107641372B (en) * | 2017-11-09 | 2021-06-08 | 安庆巨元高分子材料科技有限公司 | Preparation method of alcohol-soluble polyamide resin ink |
| EP3824022B1 (en) * | 2018-07-18 | 2024-09-11 | Basf Se | Expanded particles based on high chain-length polyamides |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS539275A (en) * | 1976-07-14 | 1978-01-27 | Yuukichi Kiuchi | Stable monooliquid emulsion and manufacture thereof |
| JPS6266991A (en) * | 1985-09-18 | 1987-03-26 | Sanyo Chem Ind Ltd | Binder and thermal transfer ink |
| JPS63280782A (en) * | 1987-05-14 | 1988-11-17 | Toray Ind Inc | Photo-setting waterless lithographic ink composition |
| US4870139A (en) * | 1985-09-16 | 1989-09-26 | Sun Chemical Corporation | Polyamide/acrylic graft copolymers |
| JPH06260536A (en) * | 1993-03-06 | 1994-09-16 | Kanegafuchi Chem Ind Co Ltd | Tape for tab |
| JPH10330449A (en) * | 1997-05-27 | 1998-12-15 | Hitachi Chem Co Ltd | Production of modified polyamideimide resin and modified polyamideimide resin |
-
2000
- 2000-01-05 CN CN00100075A patent/CN1098875C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS539275A (en) * | 1976-07-14 | 1978-01-27 | Yuukichi Kiuchi | Stable monooliquid emulsion and manufacture thereof |
| US4870139A (en) * | 1985-09-16 | 1989-09-26 | Sun Chemical Corporation | Polyamide/acrylic graft copolymers |
| JPS6266991A (en) * | 1985-09-18 | 1987-03-26 | Sanyo Chem Ind Ltd | Binder and thermal transfer ink |
| JPS63280782A (en) * | 1987-05-14 | 1988-11-17 | Toray Ind Inc | Photo-setting waterless lithographic ink composition |
| JPH06260536A (en) * | 1993-03-06 | 1994-09-16 | Kanegafuchi Chem Ind Co Ltd | Tape for tab |
| JPH10330449A (en) * | 1997-05-27 | 1998-12-15 | Hitachi Chem Co Ltd | Production of modified polyamideimide resin and modified polyamideimide resin |
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| CN1302826A (en) | 2001-07-11 |
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Granted publication date: 20030115 Termination date: 20100205 |