CN101705073B - Soybean oil-based dimeric acid type polyamide hot melt adhesive and preparation method thereof - Google Patents
Soybean oil-based dimeric acid type polyamide hot melt adhesive and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a soybean oil-based dimeric acid type polyamide hot melt adhesive and a preparation method thereof. Soybean oil-based dimeric acid, C6-C11 aliphatic dicarboxylic acid, C6-C11 aliphatic diamine, C13-C14 aromatic diamine, C6-C8 lactam, a molecular weight regulator, water and a catalyst are added into a reaction kettle for melt polycondensation action to generate the polyamide hot melt adhesive, and the prepared hot melt adhesive has the excellent physical and chemical performance of low melting point, solvent resistance, good viscosity and the like and can be used in the fields of clothes, electron, shoe industry and the like.
Description
1. technical field
The present invention relates to a kind of polyamide hot and preparation method thereof, specifically, relate to a kind of low melting point soybean oil-based dimeric acid type polyamide and preparation method thereof.
2. technical background
Polyamide hot is a kind of hot melt adhesive that aliphatic dibasic acid and diamines make by melt phase polycondensation, it has excellent in chemical performances such as heat-resisting, salt water resistance, grease resistance, also have simultaneously tensile property and wait excellent mechanical property well, be widely used in industries such as automobile, electronics, clothes.Announced multinomial patent both at home and abroad, in order to its excellent performance of further raising.
U.S. Pat 6355769 discloses with decamethylene diamine and terephthalic acid, triphenyl phosphite, N-Methyl pyrrolidone, pyridine has synthesized poly-paraphenylene terephthalamide's decamethylene diamine hot melt adhesive, its fusing point is 310.6 ℃, limiting viscosity is 0.14dL/g, water-absorbent is low, dimensional stability is good, is fit to be applied to electronics, engineering plastics and fiber product.
U.S. Pat 5,502,155 disclose with dodecane diamines and 2, and 6-naphthalene diacid, formic acid have synthesized hot melt adhesive 12N, and its fusing point is 303.4 ℃, 477.5 ℃ of decomposition temperatures, good mechanical property.
Chinese patent CN88103468A discloses with m-phthalic acid, terephthalic acid, m-phthalic acid sylvite, N, N '-dimethyl ethylidene-urea and 3,3 '-dimethyl-4,4 '-biphenyl diisocyanate has synthesized isophthaloyl paraphenylene terephthalamide-3,3 '-dimethyl-4,4 '-benzidine hot melt adhesive, fusing point is 355 ℃, can be used for preparing film, dimensional stability is good, and is high temperature resistant.
Chinese patent CN1590433 discloses with terephthalic acid, 1, and 9-nonamethylene diamine, 2-methyl isophthalic acid, 8-octamethylenediamine, phenylformic acid and sodium hypophosphite have synthesized polymeric amide type hot melt adhesive PA9T-1, and its fusing point is 306 ℃, and is heat-resisting, and the resistant to thermal aging performance is good.
Semiaromatic polyamide composition is made the engineering material owing to its excellent physics, chemical property and mechanical property are widely used.But, the resistance to low temperature of the polyamide hot that above-mentioned and so on patent is prepared is bad, fusing point is too high, be not suitable for being applied to industries such as clothes, because semiaromatic polyamide composition is insoluble in the common solvent, be unfavorable for machine-shaping owing to its degree of crystallinity height simultaneously, thereby make its range of application be subjected to very big restriction.The dimeracid that utilizes vegetable oil acid not only can be saved cost as reaction raw materials, and the while also is beneficial to environment protection and promotes the development of economy.
3. summary of the invention
The objective of the invention is to disclose a kind of soybean oil-based dimeric acid type polyamide hot melt adhesive, overcome the high defective of fusing point, to satisfy the demand of relevant industries; The preparation method of above-mentioned characteristic dimeric acid type polyamide hot melt adhesive is provided simultaneously.
The inventor finds in the process of research and preparation polyamide hot, introduces phenyl or side chain in polyamide structure, adds long carbon-chain structure and can reduce its fusing point in the hot melt adhesive structure, improves its flexility and processing forming.But the monomeric content of long carbochain surpasses the fusing point that certain limit can increase hot melt adhesive afterwards again, and the monomeric content of therefore long carbochain is moderate.By regulating the proportioning between each monomer, the order of polymer molecular structure is destroyed, have certain random degree, weakened the interaction of intermolecular hydrogen bonding, can make the hot melt adhesive of service requirements.
To be described in detail technical scheme of the present invention below.
The preparation of soybean oil-based dimeric acid type polyamide hot melt adhesive of the present invention, key are to introduce phenyl or side-chain radical in the polyamide chains segment structure, or introduce long carbochain.Described dimer acid type polyamide segmented structure is as follows:
Wherein, R
1Be two amine structures, R
2Structure be shown below
It is basic raw material that the preparation method of soybean oil-based dimeric acid type polyamide hot melt adhesive of the present invention adopts aliphatics dimeracid, aliphatic dicarboxylic acid, aliphatie diamine, aromatic diamine, lactan, with polynary monomer generation fusion copolymerization product, may further comprise the steps:
(1) earlier aliphatics dimeracid, aliphatic dicarboxylic acid, aliphatie diamine, aromatic diamine, lactan are joined respectively in the reactor, add entry, molecular weight regulator and catalyzer simultaneously, stir and feed nitrogen protection;
(2) improve temperature to 180-200 ℃, simultaneously pressure is risen to 1.0-1.5MPa, reacted 2-4 hour;
(3) pressure rises to 1.7MPa, and temperature continues to be increased to 200-250 ℃, reacts 1-1.5 hour;
(4) pressure is reduced to normal pressure, and temperature is increased to 260 ℃, continues reaction 30-60 minute;
(5) temperature is reduced to room temperature, vacuumizes 10-15 minute; Discharging.
Described soybean oil-based dimeric acid is the oleic polycondensate of plant soybean, and dimer content accounts for 75%-97%, can adopt the product of U.S. Henkel company.
Described carbonatoms is the aliphatic dicarboxylic acid of 6-11, a kind of in the diacid of selecting oneself, 2-methyl hexanodioic acid, pimelic acid, nonane diacid and the undecane diacid or more than one.
Described carbonatoms is the 6-10 aliphatie diamine, the diamines of selecting oneself, 2,4, a kind of in 4-trimethylammonium hexanediamine and the decamethylene diamine or more than one.
Described aromatic diamine is 4,4 '-diaminodiphenylmethane, 2,2 '-dimethyl diphenyl diamines, 2,2 '-dimethyl-4,4 '-diaminodiphenylmethane, 2, a kind of in two [4 (4-amino-benzene oxygen) phenyl] propane of 2-.
Select oneself a kind of in lactan, the 8-spicy inner formyl amine of described lactan can adopt the product of Henkel KGaA company or Ba Ling petro-chemical corporation.
Described molecular weight regulator is an aliphatics monoprotic acid, is selected from a kind of in acetate, propionic acid, the lauric acid.
Described catalyzer is oxyacetic acid titanium, diphosphanetetroic acid, phosphoric acid, a kind of in the triphenyl phosphite.
Gross weight in diprotic acid, diamines, monoprotic acid and lactan:
The weight of diprotic acid is the 51.4%-58.9% of gross weight
The weight of diamines is the 21.9%-35.0% of gross weight
Monacid weight is the 2.2%-3.1% of gross weight
The weight of lactan is the 9.1%-17.3% of gross weight
The mol ratio of total acid and total amine is 1.03-1.09: 1
Catalytic amount is the 0.05%-0.2%. of gross weight
Water is the 5.5%-10% of gross weight.
The measure that the present invention adopts zone heating is to solve the initial reaction stage volume big uppity problem that rises; Pressurization is to form in order to promote polymeric amide uncoiling of molecule chain crystalline, increases the intensity of product.
The invention has the advantages that:
(1) to have a fusing point low through detecting for the prepared soybean oil-based dimeric acid type polyamide hot melt adhesive of the present invention, and dimensional stability is good, salt water resistance, and advantage such as viscosity is good can be applicable to electronics, footwear already and industry such as clothes.
(2) introduce side-chain radical or phenyl or long carbochain in polymeric amide main body segment, can improve the fusing point and the flexility of polymeric amide type hot melt adhesive, melting range is at 98-120 ℃.
(3) dimeracid of the present invention is the oleic condensation polymer of plant soybean, has reduced raw materials cost, and technology is simple, also is beneficial to environment protection and promotes the development of economy.
(4) the prepared product of the present invention both can use separately, also can mix use with other products such as resin etc.Can be used with mineral filler as required, be used for the bonding of televisor electron device, or the bonding between the metallic substance, satisfy the needs of different field.
Case study on implementation
Case study on implementation 1
With 112g soybean oil-based dimeric acid (97%), 87.6g hexanodioic acid, 65.8g nonane diacid, 11.9g acetate, 103.2g decamethylene diamine, 69.3g 4,4 '-diaminodiphenylmethane, 45.2g hexanolactam, 29.7g water, 0.25g triphenyl phosphite joins in the batch condensation polymerization reactor, feeds the air in the nitrogen replacement still.Temperature is increased to 180 ℃, and pressure rises to 1.0MPa, insulation reaction 2.0 hours; Pressure continues to rise to 1.7MPa, and temperature improves 200 ℃, reacts 1 hour; Pressure is reduced to normal pressure, and temperature is increased to 260 ℃, continues reaction 30 minutes; Temperature is reduced to normal temperature, vacuumizes 10 minutes, and discharging obtains dimeric acid type polyamide hot melt adhesive, and recording fusing point is 117.5 ℃, and relative viscosity is 1.8dL/g.
Case study on implementation 2
With 112g soybean oil-based dimeric acid (97%), 24g 2-methyl hexanodioic acid, 54g undecane diacid, propionic acid 7.8g, 39.5g2,4,4-trimethylammonium hexanediamine, 31.8g 2,2 '-dimethyl diphenyl diamines, 56.4g8-spicy inner formyl amine, 17.9g water, the 0.4g diphosphanetetroic acid joins in the batch condensation polymerization reactor, feeds the air in the nitrogen replacement still.Temperature is increased to 190 ℃, and pressure rises to 1.2MPa, insulation reaction 2.5 hours; Pressure continues to rise to 1.7MPa, and temperature is increased to 210 ℃, reacts 1.2 hours; Pressure is reduced to normal pressure, and temperature is increased to 260 ℃, continues reaction 40 minutes; Temperature is reduced to normal temperature, vacuumizes 12 minutes, and discharging obtains dimeric acid type polyamide hot melt adhesive, and recording fusing point is 98 ℃,, relative viscosity is 1.3dL/g.
Case study on implementation 3
With 112g soybean oil-based dimeric acid (97%), 54.4g pimelic acid, 75.6g undecane diacid, 10.4g lauric acid, the 41g hexanediamine, 72.1g 2,2 '-dimethyl-4,4 '-diaminodiphenylmethane, 45.2g hexanolactam, 31.2g water, 0.5g phosphoric acid joins in the batch condensation polymerization reactor, feeds the air in the nitrogen replacement still.Temperature is increased to 200 ℃, and pressure rises to 1.3MPa, insulation reaction 3 hours; Pressure continues to rise to 1.7MPa, and temperature is increased to 220 ℃, continues reaction 1.3 hours; Reduce to normal pressure, temperature is increased to 260 ℃, continues reaction 50 minutes; Temperature is reduced to normal temperature, vacuumizes 15 minutes, and discharging obtains dimeric acid type polyamide hot melt adhesive, and recording fusing point is 113 ℃, and relative viscosity is 1.6dL/g.
Case study on implementation 4
With 112g soybean oil-based dimeric acid (97%), 36.5g hexanodioic acid, 56.4g nonane diacid, 8.2g acetate, 51.6g decamethylene diamine, 49.5g 2, two [4 (4-phenoxyl) phenyl] propane of 2-, 56.4g8-spicy inner formyl amine, 22.2g water, 0.5g triphenyl phosphite joins in the batch condensation polymerization reactor, feeds the air in the nitrogen replacement still.Temperature is increased to 190 ℃, and pressure rises to 1.4MPa, insulation reaction 3.5 hours; Pressure continues to rise to 1.7MPa, and temperature is increased to 230 ℃, continues reaction 1.4 hours; Reduce to normal pressure, temperature is increased to 260 ℃, continues reaction 45 minutes; Temperature is reduced to normal temperature, vacuumizes 15 minutes, and discharging obtains dimeric acid type polyamide hot melt adhesive, and recording fusing point is 109 ℃, and relative viscosity is 1.45dL/g.
Case study on implementation 5
With 112g soybean oil-based dimeric acid (75%), 73g hexanodioic acid, 72g2-methyl hexanodioic acid, 11.6g propionic acid, the 86g decamethylene diamine, 89.1g 4,4 '-diaminodiphenylmethane, 56.4g spicy inner formyl amine, 50.1g water, 1.0g oxyacetic acid titanium joins in the batch condensation polymerization reactor, feeds the air in the nitrogen replacement still.Temperature is increased to 200 ℃, and pressure rises to 1.5MPa, insulation reaction 4 hours; Pressure continues to rise to 1.7MPa, and temperature is brought up to 240 ℃, continues reaction 1.5 hours; Pressure is reduced to normal pressure, and temperature is increased to 260 ℃, continues reaction 50 minutes; Temperature is reduced to normal temperature, vacuumizes 13 minutes, and discharging obtains dimeric acid type polyamide hot melt adhesive, and recording fusing point is 120 ℃, and relative viscosity is 2.0dL/g.
Case study on implementation 6
With 112g soybean oil-based dimeric acid (75%), 65.8g nonane diacid, 97.2g undecane diacid, 14.9g lauric acid, 95.4g 2,2 '-dimethyl diphenyl diamines, 55.3g2,4,4-trimethylammonium hexanediamine, 45.2g hexanolactam, 29.2g water, 0.5g triphenyl phosphite joins in the batch condensation polymerization reactor, feeds the air in the nitrogen replacement still.Temperature is increased to 185 ℃, and pressure rises to 1.2MPa, insulation reaction 3 hours; Pressure continues to rise to 1.7MPa, and temperature rises to 250 ℃, continues reaction 1.2 hours; Pressure is reduced to normal pressure, and temperature is increased to 260 ℃, continues reaction 60 minutes; Temperature is reduced to normal temperature, vacuumizes 10 minutes, and discharging obtains dimeric acid type polyamide hot melt adhesive, and recording fusing point is 110 ℃, and relative viscosity is 1.5dL/g.
Claims (6)
1. the preparation method of a soybean oil-based dimeric acid type polyamide hot melt adhesive is characterized in that, comprises the steps:
With soybean oil-based dimeric acid, carbonatoms is that aliphatic dicarboxylic acid, the carbonatoms of 6-11 is that 6-10 aliphatie diamine, carbonatoms are that 13-14 aromatic diamine, carbonatoms join in the reactor for the 6-8 lactan, add molecular weight regulator, water and catalyzer simultaneously, under nitrogen protection, be warming up to 180-200 ℃, pressure rises to 1.0-1.5MPa, stirring reaction 2-4 hour; Continue to be warming up to 200-250 ℃, pressure is increased to 1.7MPa, reacts 1-1.5 hour; Temperature continues to be increased to 260 ℃, and pressure is reduced to normal pressure, reacts and reduces to room temperature after 30-60 minute, vacuumizes 10-15 minute; Can get the target hot melt adhesive at last;
Described molecular weight regulator is a monoprotic acid, is selected from a kind of in acetate, propionic acid or the lauric acid, and described catalyzer is oxyacetic acid titanium, diphosphanetetroic acid, phosphoric acid, a kind of in the triphenyl phosphite;
Gross weight in diprotic acid, diamines, monoprotic acid and lactan:
The weight of diprotic acid is the 51.4%-58.9% of gross weight
The weight of diamines is the 21.9%-35.0% of gross weight
Monacid weight is the 2.2%-3.1% of gross weight
The weight of lactan is the 9.1%-17.3% of gross weight
The mol ratio of total acid and total amine is 1.03-1.09: 1
Catalytic amount is the 0.05%-0.2% of gross weight
Water is the 5.5%-10% of gross weight.
2. preparation method according to claim 1 is characterized in that, described soybean oil-based dimeric acid is the oleic polycondensate of plant soybean, and dimer content accounts for 75%-97%.
3. method according to claim 1 is characterized in that, said carbonatoms is select oneself a kind of in diacid, 2-methyl hexanodioic acid, pimelic acid, nonane diacid and the undecane diacid or more than one of the aliphatic dicarboxylic acid of 6-11.
4. method according to claim 1 is characterized in that, said carbonatoms is a hexanediamine, 2,4 for the 6-10 aliphatie diamine, one or more in 4-trimethylammonium hexanediamine, heptamethylene diamine and the decamethylene diamine.
5. method according to claim 1 is characterized in that said aromatic diamine is selected from 4,4 '-diaminodiphenylmethane, 2, a kind of in 2 '-dimethyl diphenyl diamines.
6. method according to claim 1 is characterized in that, said lactan is a kind of in hexanolactam, the spicy inner formyl amine.
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| CN102559129B (en) * | 2010-12-07 | 2014-03-19 | 上海轻工业研究所有限公司 | Polyamide hot melt adhesive 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 |
| CN102863616A (en) * | 2012-06-16 | 2013-01-09 | 上海天洋热熔胶有限公司 | Preparation method of low-melting-point copolyamide hot melt adhesive |
| CN102924712A (en) * | 2012-10-18 | 2013-02-13 | 上海天洋热熔胶有限公司 | Low-melting-point polyamide hot melt adhesive with high weather resistance and preparation method thereof |
| CN103524731A (en) * | 2013-10-16 | 2014-01-22 | 上海天洋热熔胶有限公司 | Preparation method of polyamide hot melt adhesive with low surface energy for hot drills |
| CN104945274B (en) * | 2015-05-19 | 2017-01-11 | 上海化工研究院 | Novel branched fatty nylon salt, and preparation method and application thereof |
| CN107815284A (en) * | 2017-11-09 | 2018-03-20 | 山东凯恩新材料科技有限公司 | A kind of solvent-resisting blending polyamide hot and preparation method thereof |
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Address after: 201802 Shanghai City, Jiading District Hui Ping Lu Nanxiang Town, No. 505 Patentee after: Shanghai Tianyang hot melt adhesive materials Limited by Share Ltd. Patentee after: EAST CHINA University OF SCIENCE AND TECHNOLOGY Address before: 201802 Shanghai City, Jiading District Hui Ping Lu Nanxiang Town, No. 505 Patentee before: Shanghai Tianyang Hotmelt Adhesives Co.,Ltd. Patentee before: East China University of Science and Technology |
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Address after: 201802 Shanghai City, Jiading District Hui Ping Lu Nanxiang Town, No. 505 Patentee after: SHANGHAI TIANYANG HOT MELT ADHESIVE Co.,Ltd. Patentee after: EAST CHINA University OF SCIENCE AND TECHNOLOGY Address before: 201802 Shanghai City, Jiading District Hui Ping Lu Nanxiang Town, No. 505 Patentee before: Shanghai Tianyang hot melt adhesive materials Limited by Share Ltd. Patentee before: East China University of Science and Technology |
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Address after: 201802 Shanghai City, Jiading District Hui Ping Lu Nanxiang Town, No. 505 Patentee after: Tianyang New Material (Shanghai) Technology Co.,Ltd. Patentee after: EAST CHINA University OF SCIENCE AND TECHNOLOGY Address before: 201802 Shanghai City, Jiading District Hui Ping Lu Nanxiang Town, No. 505 Patentee before: SHANGHAI TIANYANG HOT MELT ADHESIVE Co.,Ltd. Patentee before: EAST CHINA University OF SCIENCE AND TECHNOLOGY |