CN1119368C - Process for preparing polyamide resin used for alcohol-soluble ink - Google Patents
Process for preparing polyamide resin used for alcohol-soluble ink Download PDFInfo
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- CN1119368C CN1119368C CN 00126683 CN00126683A CN1119368C CN 1119368 C CN1119368 C CN 1119368C CN 00126683 CN00126683 CN 00126683 CN 00126683 A CN00126683 A CN 00126683A CN 1119368 C CN1119368 C CN 1119368C
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Abstract
The present invention provides a method for preparing polyamide resin for alcohol-soluble printing ink, which is characterized in that modifying agents such as isophthalic acid (or dibasic acid thereof) and sulphonate (potassium, sodium, zinc, calcium and magnesium) are added to a reaction system for preparing the polyamide resin for alcohol-soluble printing ink by dimer acid and ethylenediamine, and consequently, the effect of improving the luster of the polyamide resin for alcohol-soluble printing ink can be achieved. The polyamide resin for alcohol-soluble printing ink prepared by the present invention can achieve the following performance indices: less than or equal to 6 (50% of an alcoholic solution by a Gaffky method) of luster, less than or equal to 5 mg KOH/g of an acid value, less than or equal to 5 mg KOH/g of an amine value, 80 cp to 150 cp of viscosity (50% of an ethanol solution), and 105 DEG C to 120 DEG C of a softening point (a whole world method), and the polyamide resin has freeze resistance (40% of an alcohol solution) that the polyamide resin can not freeze in 30 minutes at a temperature of-15 DEG C. The present invention has the characteristics of light color and high luster, and is suitable for printing ink industry.
Description
The present invention relates to a kind of polyamide resin used for alcohol-soluble ink preparation method, relate in particular to a kind of method of improving pure soluble polyamide color and luster with organic sulfonate properties-correcting agent.
In the prior art, printing ink is normally formed by vegetable fatty acids dipolymer (dimeracid) and quadrol and organic acid, amine properties-correcting agent dehydrating condensation with polyamide resin.Should possess following performance as printing ink with polyamide resin: (1) low viscosity; (2) good pure dissolubility; (3) good gloss and flowability; (4) multiple plastics film had extremely strong sticking power; (5) has good solvent release and to the compatibility of nitro-cotton; (6) good anti-freezing property and anti-gel property.Polyamide resin used for alcohol-soluble ink has reached following performance at present: color and luster≤8 (50% alcoholic solution, the Jia Shi method), acid number≤6mgKOH/g, amine value≤6mgKOH/g, viscosity (50% ethanolic soln) 50cp～160cp, 100 ℃～120 ℃ of softening temperatures (ring and ball method), frost resistance (40% ethanolic soln) :-15 ℃, do not freeze in 30 minutes.Now, people also continue to carry out correlative study work at polyamide resin softening temperature, frost resistance, gloss, better to satisfy the service requirements of high-grade printing ink." macromolecular material and science " periodical (1991,6, introduced synthetic method in 123-127) with organic-silicon-modified polyamide resin, its technology characteristics is the synthesizing organo-silicon performed polymer under catalyst action by hydroxy silicon oil and tolylene diisocyanate at first; By dimeracid, reacting ethylenediamine synthesizing polyamides performed polymer, two kinds of performed polymer blending reactions obtain the modified polyamide resin.This method has improved the softening temperature of polyamide resin, reduced congealing point again simultaneously, and organosilicon helps improving polyamide resin gloss.Its product index is: color and luster≤9 (50% alcoholic solution, Jia Shi method), acid number≤4mgKOH/g, amine value≤4mgKOH/g, viscosity (50% ethanol liquid) 50cp-100cp, 123 ℃ of softening temperatures (ring and ball method), congealing point :-4 ℃.
The object of the present invention is to provide a kind of method of polyamide resin used for alcohol-soluble ink preparation, thereby make light high gloss used for alcohol-soluble ink resin, satisfy the demand of high-grade printing ink.
The objective of the invention is to realize by following technical solution: prepare in the reaction system of polyamide resin used for alcohol-soluble ink at dimeracid and quadrol, added properties-correcting agent m-phthalic acid (or its dibasic ester) sulfonate (potassium, sodium, zinc, calcium, magnesium).In implementing process of the present invention, the mode that properties-correcting agent m-phthalic acid (or its dibasic ester) sulfonate (potassium, sodium, zinc, calcium, magnesium) can adopt elder generation and quadrol to carry out pre-reaction, also can adopt with after other organic acid mixes again with the mode of the organic amine reaction that participates in reaction system, preferred before a kind of mode.
With 1 mole dimeracid is mete-wand.Dual mode is described below respectively:
First kind of mode:
(1) in reactor with 0.8 mole～1.4 moles quadrol and 0.01 mole～0.1
M-phthalic acid (or its dibasic ester) sulfonate of mole (potassium, sodium, zinc,
Calcium, magnesium) heating reflux reaction 1 hour～3 hours, temperature of reaction is 90 ℃～130
℃, obtain sample one;
(2) in another reactor, add 1 mole of dimeracid and 0.1 mole～0.5 mole two
Unit's acid (as hexanodioic acid, sebacic acid, m-phthalic acid) and 0.1 mole～1.0
Mole monoprotic acid (as formic acid, acetate, propionic acid, ricinoleic acid, stearic acid),
Logical nitrogen, stirring are heated to 100 ℃～150 ℃, drip sample one and 0.05 and rub
That～1.0 moles of polyamines are (as hexanediamine, decamethylene diamine, diethylenetriamine, three
Ethene tetramine, tetraethylene pentamine) and 0.1 mole～1.0 moles monoamines (as
N-Butyl Amine 99, thanomin, diethanolamine), under 140 ℃～160 ℃ temperature,
Back flow reaction 0.5 hour～3 hours, the dehydration 0.5 hour that heats up gradually then～
3 hours, make temperature of reaction reach 190 ℃～240 ℃ top temperature,
Insulation reaction is 3 hours～6 hours under the top temperature;
(3) under 2.5kPa (absolute pressure), reacted again 0.5 hour～2 hours, be cooled to then
160 ℃～170 ℃ dischargings get polyamide resin used for alcohol-soluble ink.
The second way:
(1) in reactor, add 1 mole of dimeracid and 0.01 mole～0.1 mole between benzene
Dioctyl phthalate (or its dibasic ester) sulfonate (potassium, sodium, zinc, calcium, magnesium), 0.1
Mole～0.5 mole of diprotic acid (as hexanodioic acid, sebacic acid, m-phthalic acid)
And 0.1 mole～1.0 moles monoprotic acid are (as formic acid, acetate, propionic acid, castor-oil plant
Alkyd, stearic acid) logical nitrogen, open and be heated to 100 ℃～150 under the agitation condition
℃；
(2) it is polynary to drip 0.8 mole～1.4 moles quadrol and 0.05 mole～1.0 moles
Amine is (as hexanediamine, decamethylene diamine, diethylenetriamine, triethylene tetramine, tetrem
Alkene five amine) and 0.1 mole～1.0 moles monoamines (as n-Butyl Amine 99, thanomin,
Diethanolamine), under 110 ℃～160 ℃ temperature, back flow reaction 0.5 is little
Time～3 hour, the dehydration 0.5 hour～3 hours that heats up gradually then makes anti-
Answer temperature to reach 190 ℃～240 ℃ top temperature, under top temperature
Insulation reaction 3 hours～6 hours;
(3) reacted 0.5 hour～2 hours down at 2.5kPa (absolute pressure), be cooled to 160 ℃～170
℃ discharging, polyamide resin used for alcohol-soluble ink.
Compared with prior art, the present invention has following tangible advantage:
(1) polyamide resin used for alcohol-soluble ink that makes with method of the present invention can reach
Following performance index: color and luster≤6 (50% alcoholic solution, Jia Shi method); Acid number≤
5mgKOH/g; Amine value≤5mgKOH/g; Viscosity (50% ethanol liquid) 80
Cp～150cp; 105 ℃～120 ℃ of softening temperatures (ring and ball method); Frost resistance (40%
Alcoholic solution) :-15 ℃, do not freeze in 30 minutes.
(2) the present invention uses a small amount of properties-correcting agent m-phthalic acid (or its dibasic ester) sulfonic acid
Salt (potassium, sodium, zinc, calcium, magnesium) has promptly reached and has improved pure dissolubility by a relatively large margin
The printing ink purpose of polyamide resin color and luster, the look of 50% alcoholic solution of this resin
(Jia Shi method)≤6, pool can be satisfied the service requirements of high-grade printing ink well.
(3) properties-correcting agent m-phthalic acid (or its dibasic ester) sulfonate of the present invention's use
(potassium, sodium, zinc, calcium, magnesium) becomes the polymeric amide molecule with the reactive component form
A unit of chain.Both reached the purpose of utilizing the sulfonate groups modification, again not
Cause the performance that influences product in molecular weight distribution because of product.
The present invention is described further below by concrete example:
Example 1 with 1.02 moles of ethylene diamine and 0.02 mole of sodiosulfoisophthalic acid heating reflux reaction 1 hour, obtains sample 1 in reactor; In another reactor, add 1 mole of dimeracid and 0.2 mole of m-phthalic acid and 0.5 mole of stearic acid then, logical nitrogen, stirring, be heated to 150 ℃, drip sample 1 and 0.2 mole of hexanediamine and 0.5 mole of n-Butyl Amine 99 again, back flow reaction 3 hours, heat up gradually then and dewatered 5 hours, control reaction top temperature is no more than 240 ℃; Reacted 0.5 hour down at 2.5kPa (absolute pressure) at last, be cooled to 170 ℃ of dischargings, get polyamide resin used for alcohol-soluble ink.
Example 2～9 quadrols, dimeracid, m-phthalic acid (ester) sulfonate, modification diprotic acid, modification monoprotic acid, modified multicomponent amine, modification monoamine are by the metering weighing, and reaction process makes polyamide resin used for alcohol-soluble ink with example one.
Example 10 adds 1 mole of dimeracid and 0.02 mole of sodiosulfoisophthalic acid, 0.2 mole of m-phthalic acid and 0.5 mole of stearic acid in reactor, logical nitrogen, open and be heated to 120 ℃ under the agitation condition, drip 1.0 moles of ethylene diamine and 0.2 mole of hexanediamine and 0.5 molar ethanolamine, 120 ℃～140 ℃ back flow reaction 3 hours, dehydration subsequently gradually heats up, reacted 5 hours, control reaction top temperature is no more than 220 ℃, reacted 0.5 hour down at 2.5kPa (absolute pressure) at last, be cooled to 170 ℃ of dischargings, get polyamide resin used for alcohol-soluble ink.
Example 11 adds 1 mole of dimeracid and 0.03 mole of dimethyl isophthalate calcium sulphonate, 0.2 mole of hexanodioic acid and 0.5 mole of propionic acid in reactor, logical nitrogen, open and be heated to 120 ℃ under the agitation condition, drip 0.92 moles of ethylene diamine and 0.2 mole of diethylenetriamine and 0.5 mole of n-Butyl Amine 99,120 ℃～140 ℃ back flow reaction 2.5 hours, dehydration subsequently gradually heats up, reacted 5 hours, control reaction top temperature is no more than 240 ℃, reacted 1 hour down at 2.5kPa (absolute pressure) at last, be cooled to 165 ℃ of dischargings, get polyamide resin used for alcohol-soluble ink.
Example concrete raw material ratio of 1-11 and product performance index see Table 1.
Table 1 embodiment 1-11 test-results table look-up
| The test example | Raw material ratio (mol ratio) | Test-results | ||||||||||
| Quadrol | M-phthalic acid (ester) sulfonate | Dimeracid | Diprotic acid | Polyamines | Monoprotic acid | Monoamine | Acid number mgKOH/g | Amine value mgKOH/g | Softening temperature (ring and ball method) ℃ | -15 ℃ of frost resistances (40% alcoholic solution) | Color and luster (50% alcoholic solution) Jia Shi, number | |
| 1 | 1.02 | 0.02, sodium salt | 1 | 0.2, m-phthalic acid | 0.2, hexanediamine | 0.5, stearic acid | 0.5, n-Butyl Amine 99 | 4.8 | 4.9 | 107.8 | Do not freeze in 30 minutes | 6 |
| 2 | 1.0 | 0.05, methyl esters, sodium salt | 1 | 0.2, hexanodioic acid | 0.1, diethylenetriamine | 0.4, stearic acid | 0.6, n-Butyl Amine 99 | 4.3 | 5.0 | 112.5 | Do not freeze in 35 minutes | 6 |
| 3 | 1.1 | 0.1, ethyl ester, sodium salt | 1 | 0.2, sebacic acid | 0.1, hexanediamine | 0.4, propionic acid | 0.6, n-Butyl Amine 99 | 3.0 | 4.3 | 117.1 | Do not freeze in 30 minutes | 6 |
| 4 | 1.02 | 0.02, methyl esters, magnesium salts | 1 | 0.3, m-phthalic acid | 0.2, diethylenetriamine | 0.5, propionic acid | 0.5, thanomin | 3.5 | 3.6 | 120.2 | Do not freeze in 35 minutes | 6 |
| 5 | 1.15 | 0.05, ethyl ester, magnesium salts | 1 | 0.3, hexanodioic acid | 0.2, hexanediamine | 0.5, stearic acid | 0.5 | 3.0 | 4.9 | 114.5 | Do not freeze in 30 minutes | 6 |
| 6 | 1.35 | 0.1, magnesium salts | 1 | 0.3, sebacic acid | 0.1, diethylenetriamine | 0.6, stearic acid | 0.4, thanomin | 5.0 | 5.0 | 108.5 | Do not freeze in 30 minutes | 6 |
| 7 | 0.92 | 0.02, zinc salt | 1 | 0.1, m-phthalic acid | 0.1, hexanediamine | 0.4, propionic acid | 0.6, diethanolamine | 2.6 | 3.4 | 105.2 | Do not freeze in 30 minutes | 6 |
| 8 | 0.85 | 0.05, methyl esters, zinc salt | 1 | 0.1, hexanodioic acid | 0.2, diethylenetriamine | 0.5, propionic acid | 0.5, diethanolamine | 4.5 | 4.7 | 106.3 | Do not freeze in 35 minutes | 6 |
| 9 | 1.0 | 0.1, ethyl ester, zinc salt | 1 | 0.1, sebacic acid | 0.1, hexanediamine | 0.4, stearic acid | 0.6, diethanolamine | 3.8 | 4.1 | 112.3 | Do not freeze in 30 minutes | 6 |
| 10 | 1.0 | 0.02, sodium salt | 1 | 0.2, m-phthalic acid | 0.2, hexanediamine | 0.5, stearic acid | 0.5, thanomin | 5.0 | 3.6 | 116 | Do not freeze in 30 minutes | 6 |
| 11 | 0.92 | 0.03, methyl esters, calcium salt | 1 | 0.2, hexanodioic acid | 0.2, diethylenetriamine | 0.5, propionic acid | 0.5, n-Butyl Amine 99 | 4.8 | 3.8 | 105 | Do not freeze in 30 minutes | 6 |
Claims (1)
1, a kind of method for preparing polyamide resin used for alcohol-soluble ink, it is characterized in that preparing in the reaction system of polyamide resin used for alcohol-soluble ink in vegetable fatty acids dipolymer and quadrol, added properties-correcting agent, wherein properties-correcting agent is the sulfonate of m-phthalic acid sulfonate or m-phthalic acid dibasic ester, and sulfonate is sylvite, sodium salt, zinc salt, calcium salt, magnesium salts; Vegetable fatty acids dipolymer with 1 mole is a mete-wand, and preparation process comprises:
A, in reactor with the properties-correcting agent heating reflux reaction of 0.8 mole～1.4 moles quadrol and 0.01 mole～0.1 mole 1 hour～3 hours, temperature of reaction is 90 ℃～130 ℃, obtains sample one;
B, add 1 mole of vegetable fatty acids dipolymer and 0.1 mole～0.5 mole diprotic acid in another reactor, wherein diprotic acid is hexanodioic acid or sebacic acid or m-phthalic acid and 0.1 mole～1.0 moles monoprotic acid, wherein monoprotic acid is formic acid or acetate or propionic acid or ricinoleic acid or stearic acid, logical nitrogen, stir, be heated to 100 ℃～150 ℃, drip sample one and 0.05 mole～1.0 moles polyamines, wherein polyamine is hexanediamine or decamethylene diamine or diethylenetriamine or triethylene tetramine or tetraethylene pentamine and 0.1 mole～1.0 moles monoamines, wherein monoamine is n-Butyl Amine 99 or thanomin or diethanolamine, under 140 ℃～160 ℃ temperature, back flow reaction 0.5 hour～3 hours, dehydration 0.5 hour～3 hours then gradually heats up, make temperature of reaction reach 190 ℃～240 ℃ top temperature, insulation reaction is 3 hours～6 hours under top temperature;
C, be to react again under the 2.5kPa 0.5 hour～2 hours, be cooled to 160 ℃～170 ℃ dischargings then in absolute pressure, polyamide resin used for alcohol-soluble ink; Perhaps
a
1, in reactor, add 1 mole of vegetable fatty acids dipolymer and 0.01 mole～0.1 mole properties-correcting agent, 0.1 mole～0.5 mole diprotic acid, wherein diprotic acid is hexanodioic acid or sebacic acid or m-phthalic acid and 0.1 mole～1.0 moles monoprotic acid, monoprotic acid is formic acid or acetate or propionic acid or ricinoleic acid or stearic acid, logical nitrogen, opens and is heated to 100 ℃～150 ℃ under the agitation condition;
b
1, drip quadrol and 0.05 mole～1.0 moles polyamines of 0.8 mole～1.4 moles, wherein polyamine is hexanediamine or decamethylene diamine or diethylenetriamine or triethylene tetramine or tetraethylene pentamine and 0.1 mole～1.0 moles monoamines, wherein monoamine is n-Butyl Amine 99 or thanomin or diethanolamine, under 110 ℃～160 ℃ temperature, back flow reaction 0.5 hour～3 hours, dehydration 0.5 hour～3 hours then gradually heats up, make temperature of reaction reach 190 ℃～240 ℃ top temperature, insulation reaction is 3 hours～6 hours under top temperature;
c
1, absolute pressure be under the 2.5kPa reaction 0.5 hour～2 hours, be cooled to 160 ℃～170 ℃ dischargings, polyamide resin used for alcohol-soluble ink.
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| CN 00126683 CN1119368C (en) | 2000-11-14 | 2000-11-14 | Process for preparing polyamide resin used for alcohol-soluble ink |
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| CN 00126683 CN1119368C (en) | 2000-11-14 | 2000-11-14 | Process for preparing polyamide resin used for alcohol-soluble ink |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6960248B2 (en) * | 2003-05-22 | 2005-11-01 | Arizona Chemical Company | Cyclic bisamides useful in formulating inks for phase-change printing |
| CN103554485A (en) * | 2013-10-30 | 2014-02-05 | 安庆市虹泰新材料有限责任公司 | Preparation method of transparent dimer acid type polyamide resin |
| CN103554486B (en) * | 2013-10-30 | 2016-01-06 | 安庆市虹泰新材料有限责任公司 | A kind of preparation method of alcohol dissolubility dimer acid type polyamide resin |
| CN104788671A (en) * | 2015-04-30 | 2015-07-22 | 河北利晖生物科技股份有限公司 | Preparation method of environment-friendly high-hardness alcohol-soluble polyamide resin |
| CN108148200A (en) * | 2016-12-02 | 2018-06-12 | 上海杰事杰新材料(集团)股份有限公司 | Water-soluble polyamide resins and preparation method thereof |
| 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 |
| CN111234208B (en) * | 2020-04-01 | 2021-07-16 | 中山大学 | Polyester/polyamide copolymer and preparation method and application thereof |
| CN115594989A (en) * | 2022-11-28 | 2023-01-13 | 宇虹颜料股份有限公司（Cn） | Preparation method of polyamide pigment preparation |
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