CN104788671A - Preparation method of environment-friendly high-hardness alcohol-soluble polyamide resin - Google Patents
Preparation method of environment-friendly high-hardness alcohol-soluble polyamide resin Download PDFInfo
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- CN104788671A CN104788671A CN201510214821.XA CN201510214821A CN104788671A CN 104788671 A CN104788671 A CN 104788671A CN 201510214821 A CN201510214821 A CN 201510214821A CN 104788671 A CN104788671 A CN 104788671A
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Abstract
The invention discloses a preparation method of an environment-friendly high-hardness alcohol-soluble polyamide resin, which comprises the following steps: adding dimer acid into a reaction kettle, sucking monobasic acid into the reaction kettle through vacuum, heating to 70-90 DEG C while stirring, slowly and dropwisely adding diamine and hydroxy diamine into the reaction kettle in sequence, stirring for 10-20 minutes, heating to 130-170 DEG C, stirring for 0.5-1.5 hours, continuing heating to 170-190 DEG C, stirring for 0.5-1.5 hours, continuing heating to 200-230 DEG C, stirring for 1-2 hours, vacuumizing, reacting for 0.5-1.5 hour, cooling to 190-210 DEG C, adding an antioxidant, stirring for 5-15 minutes, and discharging. The environment-friendly high-hardness alcohol-soluble polyamide prepared by the method has excellent solvent release property. The ink prepared from the resin has the characteristics of high volatilization speed and bright color. The paint film has the characteristics of favorable hardness, low friction factor, favorable antisticking property and the like.
Description
Technical field
The present invention relates to a kind of preparation method of polyamide resin, be specifically related to a kind of preparation method of environment-friendly type high rigidity alcohol-soluble polyamide resin.
Background technology
Polyamide resin, is the broad-spectrum industrial chemicals of excellent property, has good over-all properties, comprise mechanical property, thermotolerance, wearability, chemical proofing and self lubricity, and frictional coefficient is low, have certain flame retardant resistance.Polyamide resin is widely used in ink area because of its characteristic property, and existing Polyamide Resins for Printing Ink is in alcoholic solvent, and solubleness is poor, so also need to add a certain amount of as the aromatic solvent such as benzene, toluene.Along with the reinforcement of environmental consciousness, numerous and confused requirement has the polyamide resin of complete alcohol dissolubility, although current domestic more existing reports about alcohol-soluble polyamide resin, but ubiquity color is darker, poor transparency, gel tendency is serious, the problems such as the restorative difference of gel.CN103554486A discloses a kind of preparation method of alcohol dissolubility dimer acid type polyamide resin, and it is mainly through adding properties-correcting agent to change the solvability of polyamide resin, but difference of hardness after making ink, and anti-reflective viscosity is poor.
In view of this, the preparation method inventing a kind of environment-friendly type high rigidity alcohol-soluble polyamide resin is needed, to make up the deficiencies in the prior art.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of environment-friendly type high rigidity alcohol-soluble polyamide resin.
To achieve these goals, the technical solution used in the present invention is as follows:
A preparation method for environment-friendly type high rigidity alcohol-soluble polyamide resin, it comprises the steps:
Dimeracid is put in reactor, again monoprotic acid is passed through in vacuum sucting reaction still, be heated with stirring to 70-90 DEG C, the diamine of diamine and hydroxyl is slowly added drop-wise in reactor successively, stir 10-20 minute, be warming up to 130-170 DEG C, stir 0.5-1.5 hour, continue to be warming up to 170-190 DEG C, stir 0.5-1.5 hour, temperature continues to be elevated to 200-230 DEG C, stir 1-2 hour, vacuumize reaction 0.5-1.5 hour, be cooled to 190-210 DEG C, add oxidation inhibitor and stir 5-15 minute, discharging, obtain environment-friendly type high rigidity alcohol-soluble polyamide resin,
Described monoprotic acid bag is selected from the one in acetic acid or propionic acid, described diamine be selected from quadrol, 1,3-propylene diamine, butanediamine, pentamethylene diamine and hexanediamine one or more;
The weight percentage that each raw material accounts for gross weight is as follows:
Dimeracid 75-88.3%;
Monoprotic acid 3-11%;
Diamine 8-16%;
The diamine 0.6-1.4% of hydroxyl;
Oxidation inhibitor 0.1-0.3%.
Further improve as the present invention, described step is specific as follows:
Dimeracid is put in reactor, then by monoprotic acid by vacuum sucting reaction still, is heated with stirring to 80 DEG C, the diamine of diamine and hydroxyl is slowly added drop-wise in reactor successively, stirs 15 minutes, be warming up to 150 DEG C, stir 1 hour, continue to be warming up to 180 DEG C, stir 1 hour, temperature continues to be elevated to 215 DEG C, stirs 1.5 hours, vacuumizes reaction 1 hour, be cooled to 200 DEG C, add oxidation inhibitor and stir 10 minutes, discharging, obtain environment-friendly type high rigidity alcohol-soluble polyamide resin.
Further improve as the present invention, the weight percentage that described each raw material accounts for gross weight is as follows:
Dimeracid 79.9%;
Monoprotic acid 6.9%;
Diamine 12.0%;
The diamine 1% of hydroxyl;
Oxidation inhibitor 0.2%.
Further improve as the present invention, described monoprotic acid is selected from propionic acid.
Further improve as the present invention, described diamine is selected from quadrol and 1,3-propylene diamine, and 6.9%, 1, the 3-propylene diamine that the weight of quadrol accounts for gross weight accounts for 5.1% of gross weight.
Further improve as the present invention, the diamine of described hydroxyl is IPDA.
Further improve as the present invention, described oxidation inhibitor is antioxidant 1010.
In order to find the polyamide resin of alcohol dissolubility, present inventor has done a large amount of research work, find polyamide resin, owing to lacking hydrophilic group in the molecule, so solvability is poor in the alcohol that polarity is stronger, by changing the size of molecular weight, although the acid number of polyamide resin changes its solvability in alcohol to a certain extent, it still can not be made to dissolve completely.Find to introduce hydroxyl diamine chain link in the molecule between contriver is accidental.The molecule of solvent alcohol and the effect of polyamide resin can be strengthened, impel polyamide resin to dissolve in alcoholic solvent.
When contriver is surprised at this discovery, but find because the introducing of hydroxyl diamine makes the chemical structure of polyamide resin there occurs change, be applied in ink and need to do larger adjustment to the formula of ink, make the use of polyamide resin provided by the present invention limited, the present inventor has carried out larger adjustment by creative work to feed composition, finally make present method be prepared into the polyamide resin obtained and possess more excellent and gratifying performance, and the polyamide resin making the application provide has the technical indicator with conventional resins with substantially identical macroscopic view.Based on above research and creation, define technical scheme of the present invention, obtain environment-friendly type high rigidity alcohol-soluble polyamide resin LH-6399.
Compared with prior art, the beneficial effect that the present invention obtains is:
The environment-friendly type high rigidity alcohol soluble polyamide prepared by the inventive method has splendid solvent release, has evaporation rate fast by the ink of this resin manufacture, bright in colour, the features such as hardness of paint film is good, frictional coefficient is low, anti-reflective viscosity is good.The product using present method to obtain, can reduce soluble cotton consumption.
Environment-friendly type high rigidity alcohol-soluble polyamide resin of the present invention makes ink, possesses high rigidity and low-friction coefficient after film forming, and anti-reflective viscosity can be good.
The polyamide resin stocked by the inventive method can reach following index: color and luster≤6 (Fe-Co); Acid number≤5mgKOH/g; Amine value≤5mgKOH/g; Viscosity (50% solid content, 95% dissolve with ethanol) 120 cP-140cP; Softening temperature (ring and ball method) 100-200 DEG C.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in more detail.
Embodiment 1
First 79.9g dimeracid (Li Hui bio tech ltd, Hebei) is dropped into reactor, temperature 80 DEG C, then 6.9g propionic acid is passed through vacuum sucting reaction pot, temperature 80 DEG C, drive agitator, by 6.9g quadrol and 5.1g 1, the mode of 3 propylene diamine by dripping, slowly add reactor, then again 1g isophorone diamine (IPDA) is slowly added, add rear stirring and after 15 minutes, convince deep fat turnover valve by patient analysis, be warming up to 150 DEG C, close thermal oil fuel charging valve when material temperature reaches 150 DEG C, be incubated one hour.Then convince deep fat fuel charging valve by patient analysis to continue to be warming up to 180 DEG C, be incubated 1 hour, temperature continues to rise to 215 DEG C, closes heat conduction fuel tap, is incubated 1.5 hours.Vacuumize (-0.1Mpa) and react 1 hour, open cooling turnover valve, be cooled to 200 DEG C, add 0.2g antioxidant 1010 and stir 10 minutes, discharging both obtained.
Embodiment 2
First 75g dimeracid (Li Hui bio tech ltd, Hebei) is dropped into reactor, temperature 70 C, then 8g propionic acid is passed through vacuum sucting reaction pot, temperature 70 C, drive agitator, by 8.2g quadrol and 7.1g 1, the mode of 3 propylene diamine by dripping, slowly add reactor, then again 1.4g isophorone diamine (IPDA) is slowly added, add rear stirring and after 15 minutes, convince deep fat turnover valve by patient analysis, be warming up to 150 DEG C, close thermal oil fuel charging valve when material temperature reaches 150 DEG C, be incubated one hour.Then convince deep fat fuel charging valve by patient analysis to continue to be warming up to 180 DEG C, be incubated 1 hour, temperature continues to rise to 215 DEG C, closes heat conduction fuel tap, is incubated 1.5 hours.Vacuumize (-0.1Mpa) and react 1 hour, open cooling turnover valve, be cooled to 200 DEG C, add 0.3g antioxidant 1010 and stir 10 minutes, discharging both obtained.
Embodiment 3
First 88.3g dimeracid (Li Hui bio tech ltd, Hebei) is dropped into reactor, temperature 80 DEG C, then 3g propionic acid is passed through vacuum sucting reaction pot, temperature 80C, drive agitator, by 4.7g quadrol and 3.3g 1, the mode of 3 propylene diamine by dripping, slowly add reactor, then again 0.6g isophorone diamine (IPDA) is slowly added, add rear stirring and after 15 minutes, convince deep fat turnover valve by patient analysis, be warming up to 150 DEG C, close thermal oil fuel charging valve when material temperature reaches 150 DEG C, be incubated one hour.Then convince deep fat fuel charging valve by patient analysis to continue to be warming up to 180 DEG C, be incubated 1 hour, temperature continues to rise to 215 DEG C, closes heat conduction fuel tap, is incubated 1.5 hours.Vacuumize (-0.1Mpa) and react 1 hour, open cooling turnover valve, be cooled to 200 DEG C, add 0.1g antioxidant 1010 and stir 10 minutes, discharging both obtained.
Comparative example 1 adds diethanolamine
First 79.9g dimeracid (Li Hui bio tech ltd, Hebei) is dropped into reactor, temperature 80 DEG C, then 6.9g propionic acid is passed through vacuum sucting reaction pot, temperature 80 DEG C, drive agitator, the mode by dripping by 6.9g quadrol and 5.1g 1,3 propylene diamine, slowly add reactor, then again 1g diethanolamine is slowly added, add rear stirring and after 15 minutes, convince deep fat turnover valve by patient analysis, be warming up to 150 DEG C, close thermal oil fuel charging valve when material temperature reaches 150 DEG C, be incubated one hour.Then convince deep fat fuel charging valve by patient analysis to continue to be warming up to 180 DEG C, be incubated 1 hour, temperature continues to rise to 215 DEG C, closes heat conduction fuel tap, is incubated 1.5 hours.Vacuumize (-0.1Mpa) and react 1 hour, open cooling turnover valve, be cooled to 200 DEG C, add 0.2g antioxidant 1010 and stir 10 minutes, discharging both obtained.
Comparative example 2
First 79.9g dimeracid (Li Hui bio tech ltd, Hebei) is dropped into reactor, temperature 80 DEG C, then passes through vacuum sucting reaction pot by 6.9g propionic acid, temperature 80 DEG C, drive agitator, 6.9g quadrol and 5.1g hexanediamine are passed through the mode dripped, slowly add reactor, then again 1g diethanolamine is slowly added, add rear stirring and after 15 minutes, convince deep fat turnover valve by patient analysis, be warming up to 150 DEG C, close thermal oil fuel charging valve when material temperature reaches 150 DEG C, be incubated one hour.Then convince deep fat fuel charging valve by patient analysis to continue to be warming up to 180 DEG C, be incubated 1 hour, temperature continues to rise to 215 DEG C, closes heat conduction fuel tap, is incubated 1.5 hours.Vacuumize (-0.1Mpa) and react 1 hour, open cooling turnover valve, be cooled to 200 DEG C, add 0.2g antioxidant 1010 and stir 10 minutes, discharging both obtained.
Effect example 1
To embodiment 1-3, and the polyamide resin that comparative example 1 and 2 obtains carries out Performance Detection, and its medium viscosity and color and luster are 50% solid part, and solvent is 95% ethanol.Specifically in table 1:
Polyamide resin that the inventive method provides possesses good alcohol dissolubility, and preferably performance.
The above embodiment is only the preferred embodiments of the present invention, and and the feasible enforcement of non-invention exhaustive.For persons skilled in the art, to any apparent change done by it under the prerequisite not deviating from the principle of the invention and spirit, all should be contemplated as falling with within claims of the present invention.
Claims (7)
1. a preparation method for environment-friendly type high rigidity alcohol-soluble polyamide resin, is characterized in that, it comprises the steps:
Dimeracid is put in reactor, again monoprotic acid is passed through in vacuum sucting reaction still, be heated with stirring to 70-90 DEG C, the diamine of diamine and hydroxyl is slowly added drop-wise in reactor successively, stir 10-20 minute, be warming up to 130-170 DEG C, stir 0.5-1.5 hour, continue to be warming up to 170-190 DEG C, stir 0.5-1.5 hour, temperature continues to be elevated to 200-230 DEG C, stir 1-2 hour, vacuumize reaction 0.5-1.5 hour, be cooled to 190-210 DEG C, add oxidation inhibitor and stir 5-15 minute, discharging, obtain environment-friendly type high rigidity alcohol-soluble polyamide resin,
Described monoprotic acid bag is selected from the one in acetic acid or propionic acid, described diamine be selected from quadrol, 1,3-propylene diamine, butanediamine, pentamethylene diamine and hexanediamine one or more;
The weight percentage that each raw material accounts for gross weight is as follows:
Dimeracid 75-88.3%;
Monoprotic acid 3-11%;
Diamine 8-16%;
The diamine 0.6-1.4% of hydroxyl;
Oxidation inhibitor 0.1-0.3%.
2. the preparation method of a kind of environment-friendly type high rigidity alcohol-soluble polyamide resin according to claim 1, it is characterized in that, described step is specific as follows:
Dimeracid is put in reactor, then by monoprotic acid by vacuum sucting reaction still, is heated with stirring to 80 DEG C, the diamine of diamine and hydroxyl is slowly added drop-wise in reactor successively, stirs 15 minutes, be warming up to 150 DEG C, stir 1 hour, continue to be warming up to 180 DEG C, stir 1 hour, temperature continues to be elevated to 215 DEG C, stirs 1.5 hours, vacuumizes reaction 1 hour, be cooled to 200 DEG C, add oxidation inhibitor and stir 10 minutes, discharging, obtain environment-friendly type high rigidity alcohol-soluble polyamide resin.
3. the preparation method of a kind of environment-friendly type high rigidity alcohol-soluble polyamide resin according to claim 1, it is characterized in that, the weight percentage that described each raw material accounts for gross weight is as follows:
Dimeracid 79.9%;
Monoprotic acid 6.9%;
Diamine 12.0%;
The diamine 1% of hydroxyl;
Oxidation inhibitor 0.2%.
4. the preparation method of a kind of environment-friendly type high rigidity alcohol-soluble polyamide resin according to any one of claim 1-3, it is characterized in that, described monoprotic acid is propionic acid.
5. the preparation method of a kind of environment-friendly type high rigidity alcohol-soluble polyamide resin according to any one of claim 1-3, it is characterized in that, described diamine is quadrol and 1,3-propylene diamine, 6.9%, 1, the 3-propylene diamine that the weight of quadrol accounts for raw material gross weight accounts for 5.1% of raw material gross weight.
6. the preparation method of a kind of environment-friendly type high rigidity alcohol-soluble polyamide resin according to any one of claim 1-3, is characterized in that, the diamine of described hydroxyl is isophorone diamine.
7. the preparation method of a kind of environment-friendly type high rigidity alcohol-soluble polyamide resin according to any one of claim 1-3, it is characterized in that, described oxidation inhibitor is antioxidant 1010.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510214821.XA CN104788671A (en) | 2015-04-30 | 2015-04-30 | Preparation method of environment-friendly high-hardness alcohol-soluble polyamide resin |
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| CN201510214821.XA CN104788671A (en) | 2015-04-30 | 2015-04-30 | Preparation method of environment-friendly high-hardness alcohol-soluble polyamide resin |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107652431A (en) * | 2017-11-09 | 2018-02-02 | 安庆巨元高分子材料科技有限公司 | One kind modeling printing ink alcohol-soluble polyamide resin and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1353128A (en) * | 2000-11-14 | 2002-06-12 | 巴陵石化岳阳石油化工总厂 | Process for preparing polyamide resin used for alcohol-soluble ink |
| CN103113577A (en) * | 2013-02-05 | 2013-05-22 | 苏州瀚海化学有限公司 | Alcohol-soluble copolyamide and preparation method thereof |
| CN103554486A (en) * | 2013-10-30 | 2014-02-05 | 安庆市虹泰新材料有限责任公司 | Preparation method of alcohol-soluble dimer acid type polyamide resin |
-
2015
- 2015-04-30 CN CN201510214821.XA patent/CN104788671A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1353128A (en) * | 2000-11-14 | 2002-06-12 | 巴陵石化岳阳石油化工总厂 | Process for preparing polyamide resin used for alcohol-soluble ink |
| CN103113577A (en) * | 2013-02-05 | 2013-05-22 | 苏州瀚海化学有限公司 | Alcohol-soluble copolyamide and preparation method thereof |
| CN103554486A (en) * | 2013-10-30 | 2014-02-05 | 安庆市虹泰新材料有限责任公司 | Preparation method of alcohol-soluble dimer acid type polyamide resin |
Non-Patent Citations (1)
| Title |
|---|
| 杨鸣波 等: "《中国材料工程大典.第6卷.高分子材料工程（上）》", 31 March 2006, 化学工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107652431A (en) * | 2017-11-09 | 2018-02-02 | 安庆巨元高分子材料科技有限公司 | One kind modeling printing ink alcohol-soluble polyamide resin and preparation method thereof |
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Application publication date: 20150722 |