CN101570678B - Method for preparing hot melt adhesive for high-polymer material lining cloth - Google Patents
Method for preparing hot melt adhesive for high-polymer material lining cloth Download PDFInfo
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- CN101570678B CN101570678B CN2009100993780A CN200910099378A CN101570678B CN 101570678 B CN101570678 B CN 101570678B CN 2009100993780 A CN2009100993780 A CN 2009100993780A CN 200910099378 A CN200910099378 A CN 200910099378A CN 101570678 B CN101570678 B CN 101570678B
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Abstract
The invention discloses a method for preparing the hot melt adhesive for high-polymer material lining cloth, which is obtained through regulating the constitution of copolymerization units by controlling the temperature and pressure in the processes of transesterification reaction, esterification and amidation reaction and co-polycondensation reaction in the presence of nano-silica. The hot melt adhesive has the advantages of lower melting temperature, good adhesive strength and high resistance to washing and dry-cleaning.
Description
Technical field
The present invention relates to a kind of preparation method of hot melt adhesive for high-polymer material lining cloth.
Background technology
A kind of preparation method of polyesteramide thermosol for fabric is all disclosed in JP59-140226, US4604449, US4345064 and US4254254.They have all adopted different di-carboxylic acid (or its ester), divalent alcohol or diamine, and under catalyst action, heated and stirred is carried out transesterification reaction, at high temperature carry out polycondensation then and make.And the thermal state high strength hot melt adhesive of a kind of polymeric amide or polyester amide structure is also disclosed among the CN1215746A, and they are in the time of 60 ℃, and the hot stripping strength of T type of PE/PE is＞600N/25mm, in the time of 70 ℃, can remain on＞level of 300N/25mm.
With respect to the hot melt adhesive in these patents; The application's hot melt adhesive has lower melt temperature; Thereby can under lesser temps and pressure, carry out coating and press scald processing, and not damage fiber and cause influencing feel, the application's hot melt adhesive also has excellent bonding strength; And had the anti-dry-cleaning more than 20 times of copolyamide concurrently, laundry-resistant " dual " characteristic that modified poly ester is fabulous.
Summary of the invention
The objective of the invention is to overcome weak point of the prior art, and a kind of preparation method of hot melt adhesive for high-polymer material lining cloth is provided.
The object of the invention can obtain through following measure:
1. the key factors such as proportioning of screening reaction raw materials and stock yard come the polyesteramide molecular structure is carried out scientific design, obtain best production technique thus.
Branch clamp mechanism through for polyesteramide (PEA) carries out scientific and reasonable design, can make PEA have proper fusing point and molecular weight, and the crystallization rounding, and is soft, and high stripping is strong, characteristics such as anti-strong washing.
The polymerization degree is very little for the influence of its fusing point, thereby the principal element that influences the fusing point of polyesteramide is that the ratio of each integral part changes.Through computing software, set up the mathematical model between hot melt adhesive fusing point and the component, according to this calculated with mathematical model; Draw out the triangular diagram of fusing point and component relation, the foundation of this mathematical model can calculate the prescription of different hot melt adhesives according to the different user needs, trial production checking in the warp; The mathematical model estimation result is very satisfied; Carry out proportioning reaction by ester group and carboxamido-group, add a certain amount of basic auxiliary agent simultaneously, when molecular weight greater than after to a certain degree; Depend on the high molecular fusing point difference of a kind of crystallization and the degree of crystalline integrity to depend on common chain structure and aggregated structure in fact.When the ratio of ester group/carboxamido-group is 2.5: 1, after ester group/carboxamido-group reaction, particularly in reaction process, carry out increase-volume, can produce some new chain links, and cause the variation of each crystallization macromolecule aggregation attitude.Product is clear state under the condition of high temperature, melt flow rate(MFR) reaches the suitable polymeric degree that was product at 35 o'clock.
Above-mentioned research shows, when ester group reduces in system, makes fusing point that downtrending arranged.This is the existence owing to ester group, has obstructed the normal growth of its strand crystallization, this shows that proportioning is the main factor that influences fusing point.
PEA is a crystalline material; But owing to exist crystalline region and non-crystalline region simultaneously in the imperfect crystal system; According to adhesive Theory, the existence of nucleus will make the cohesive strength of hot melt adhesive rise, and interface affinity descends; Therefore we adopt random copolymerization amorphous nylons as tackiness agent, improve the crystal property of product through the adjustment of starting with of following three kinds of approach.
A reduces percent crystallinity;
B regulates the ratio of crystalline region and non-crystalline region through random copolymerization;
C introduces the monomer that contains side chain or ring structure, the regularity of saboteur's chain.
Temperature of reaction is in the time of 130 ℃～140 ℃, and PEA esterification amidate action 1 hour 20 minutes just has water to generate.Decline along with the reactive functional group degree; The raising of viscosity, the reduction of acid concentration is in the 2 hour reaction times in later stage; We come strict control fractionation cat head Wen Wendu (below≤120 ℃) in the method for having taked on the technology progressively to improve concentration; This continues reaction with regard to having guaranteed the divalent alcohol in the system not run off, water byproduct is got to discharge in time, has kept the stable ratio of alcohol, acid, nylon 66, diamine.
For the strict control of the temperature of reaction of esterification and amidate action, guaranteed the consistence of reaction conditions in addition, made the fusing point of polyesteramide like this, molecular weight favorable reproducibility, stable performance.Simultaneously, reduce second-order transition temperature, made bonding place stress be easy to disperse to reach the minimum steady state of internal stress, thereby improve bond strength and penetrating quality, guaranteed bonding strength and kindliness.Suitably improve molten finger, melt viscosity can reduce slightly, and thermal fluidity improves, and helps infiltration and the diffusion of hot melt adhesive to fabric.
Polyesteramide copolycondensation process is thermo-negative reaction.(Δ H＞0) reaction equilibrium constant is to increase along with the raising of temperature, yet, after the raising temperature of reaction; The viscosity of reactant constantly increases, and molecular weight also improves comparatively fast, usually under this condition; The equilibrium constant of polycondensation is all smaller, and polycondensation is generally all at high temperature carried out, so at high temperature exist reversible reaction simultaneously; DeR and permutoid reaction, the reversibility of reaction is bigger.In order to reduce these side reactions, in the later stage of reaction, adopt the method that suitably reduces temperature of reaction, this method effect is relatively good, under the situation that does not increase the reaction times, has obtained the product of higher molecular weight.
On molecular chain, embedded the low building block of excellent performance; Upset the order structure of molecule, increased structural flexibility, help motion of molecule or segmental and swing; Make two kinds of molecules in the system be easy to each other near and produce magnetism; Reduce the probability that hydrogen bond forms, and reduced crystallinity of polymer thus, thereby reduced the fusing point of polyesteramide.
Through reducing the ratio of the hydrophilic radical in the molecular chain structure in the material, help to reduce the water-intake rate of material, improve the wash durability of product.And contain a large amount of amide groups in the nylon molecular chain.Be easy to cloth in fiber form hydrogen bond, guaranteed the bond strength of sizing material.Simultaneously, amide group is again a polar group, makes its performance with good drug-resistant and reagent, and reaches dry cleaning resistance ability preferably.
On the basis of this above-mentioned research, we have introduced homologue and a kind of particle form additive of nylon 12 especially, have adjusted the content ratio of amide group in the polymkeric substance.
The introducing of this additive can be so that low-molecular-weight ester and acid amides carry out interlinkage esterification the time, but its molecular structure does not impact next step polycondensation.The interpolation of this material has realized in the esterification process of polyester the Chemical bond with the nylon molecule, adjusts and improved simultaneously the kindliness and the anti-dry-cleaning ability of product again.
2. used special CPD catalyzer, i.e. the nanometer titanium dioxide Si catalyst:
The kind of catalyzer and the quality of grade can directly influence the speed of chemical reaction and the tone of product.In order to make polyesteramide that outward appearance and economy preferably arranged, guarantee transesterify, the esterification amidate action fully, steadily, the screening of catalyst test through a large amount of obtains a kind of special high activated catalyst CPD, i.e. the nanometer titanium dioxide Si catalyst.
Said high activated catalyst CPD, it is a kind of nanometer SiO
2Material, its particle diameter be less than 10 nanometers, and they are different with nano material within general 100 nanometer range, and particle diameter is littler, purchases Shanghai, white Shanghai titanizing worker ltd.This catalyzer suitability is big, need not to add acid ester salt class catalyzer and other auxiliary agent again, before having saved copolycondensation in the operation, opens the step that system adds catalyzer, and has avoided that oxygen gets in the reactive system under the high temperature.This catalyzer is insensitive to acidic-group, and the concentration of its reactive behavior and hydroxyl is inversely proportional to, because copolycondensation later stage hydroxyl is fewer and feweri, activity of such catalysts progressively rises along with the carrying out of reaction and improves.
3, the vacuum tightness of raising reactive system is strengthened the high purity of copolycondensation:
2 hours of beginning of copolycondensation, because middle lower molecular weight is many, vacuum tightness should not promote too fast; Otherwise the liquid flooding phenomenon can appear; Can influence the quality of production and product when serious, up to 2 hours 30 minutes the later stage that polyreaction finishes, the vacuum tightness of system is high more good more after 2 hours.During reaction, vacuum tightness requires to reach 5～10mmHg.
The application discloses a kind of preparation method of hot melt adhesive for high-polymer material lining cloth, and its concrete technical process is:
Feed intake → transesterification reaction → feed intake → esterification amidate action → copolycondensation → system in pre-cooled → discharging → cooling → fragmentation → dry → deep cooling pulverizing → sub-sieve → packing → finished product
It specifically comprises following process step:
(1) transesterification reaction:
Join raw material terephthalate, divalent alcohol, nanometer titanium dioxide Si catalyst among the reaction kettle;, fully stirs reactor temperature material when reaching 140 ℃; Progressively be warmed up to 150～180 ℃, gas phase temperature remains on 60～80 ℃, accomplishes up to permutoid reaction;
(2) esterification amidate action:
After reducing the temperature to 130～150 ℃ to above-mentioned product of transesterification reaction; Add diprotic acid, diamine and nylon 12 homologues, the rising temperature of reaction is at 180～220 ℃, and the cat head gas phase temperature reacts at 100～120 ℃; During reaction, feed rare gas element and be added on protection;
(3) copolycondensation:
Progressively improve temperature of reaction to 240～260 ℃, carry out progressively to reactive system that extracting air reduces pressure simultaneously, prevent on the material liquid generally, polyreaction is after 3 hours; Vacuum tightness is brought up to≤5mmHg, the working current of the viscosity useable electric moter of material is weighed, when electric current reaches 9-12A; During preferred 10.5A, this moment, the product melt flow rate(MFR) reached 30-38g/10min, preferred 35g/10min; Can think and the reaction completion feed rare gas element, blowing.
In step 1, divalent alcohol is 1, the 4-butyleneglycol.The mol ratio of DMT. Dimethyl p-benzenedicarboxylate and divalent alcohol is 1: 0.9～1: 1.5, is preferably 1: 1.2.
In step 1, the nano silicon catalyst particle size is less than 10 nanometers, and they are different with nano material within general 100 nanometer range, and particle diameter is littler, and available from Shanghai, Shanghai titanizing worker ltd, its additional proportion is the 0.02wt% of material gross weight.
In step 2; Diprotic acid can be selected from one or more in sebacic acid, SL-AH, tridecanyldicarboxylic acid, 15 carbon dicarboxylic acids, 17 carbon dicarboxylic acids; Preferred sebacic acid, diamine is selected from one or more in decamethylene diamine, nonamethylene diamine, the dodecyl diamine, preferred decamethylene diamine.
The mol ratio of terephthalate and nylon 12 homologues is 1: 0.001-1: 0.01, be preferably 1: 0.002.
In step 2, the mol ratio of DMT. Dimethyl p-benzenedicarboxylate and diamine is 1: 0.1-1: 0.3, be preferably 1: 0.23, and the mol ratio of terephthalate and diprotic acid is 1: 0.1-1: 0.3, be preferably 1: 0.25.
In step 2, the scope of temperature and pressure is generally 0.3MPa-0.05MPa.
The application also discloses a kind of hot melt adhesive for high-polymer material lining cloth that obtains through method for preparing thus.It has than low melting glass, excellent bonding strength, good anti-dry-cleaning and washing performance.
Hot melt adhesive for high-polymer material lining cloth among the application can be used for lining cloth production aspect, is particularly suitable for producing to anti-dry-cleaning with to the water-fast PADING CLOTH that all has certain requirements of washing.
Listing embodiment below further specifies.
Embodiment
One. the raw material explanation:
Nano silicon: particle diameter is less than 10nm, available from Shanghai, Shanghai titanizing worker ltd.
DMT. Dimethyl p-benzenedicarboxylate:
Iran produces DMT. Dimethyl p-benzenedicarboxylate (DMT), Dimethyl terephthalate, C
10H
10O
4, molecular weight 194.18, content: 99.90%.
Divalent alcohol: by 1 of South Asia, Taiwan chemical industry ltd production, 4-butyleneglycol.
Two. testing method:
1. outward appearance
Appearance method.
2. melting range
Pressing GB/T 4608 methods carries out.
3. melt flow rate(MFR)
Press thermoplastics melt flow rate(MFR) TP execution among the GB/T 3682, choice criteria membrana oralis internal diameter is 2.095mm, and test temperature and load see the following form.If load is not 21.18N, then being converted into the numerical value that records at this test temperature and load again is the actual value under the 21.18N condition.
Test conditions
The result calculates
Melt flow rate(MFR) can be calculated as follows:
In the formula:
The MFR--melt flow rate(MFR), unit is per 10 minutes (g/10min) of gram;
M-cuts the arithmetical av of batten quality, and unit is gram (g);
T--cuts the timed interval, and unit is second (s).
If instrument has automatic timing unit, also can be calculated as follows:
In the formula:
MFR---melt flow rate(MFR), unit is per 10 minutes (g/10min) of gram;
D---charging basket diameter, unit are centimetre (cm);
The fusant density of ρ---hot melt adhesive, unit is every cubic centimetre of (g/cm of gram
3);
H---piston rod stroke distances, unit is centimetre (cm);
T---the used time of piston rod stroke distances, unit is second (S).
4. stripping strength
Pressing FZ/T01085-2000 " hot molten binding lining strong test method for peeling " carries out.
5. the conservation rate of decaying:
Initial bonding strength A tests according to FZ/T01085-2000 " hot molten binding lining strong test method for peeling ".
Washing or dry-cleaning back stripping strength B are according to FZ/T01085-2000 " hot molten binding lining strong test method for peeling ";
Embodiment 1
(1) transesterification reaction:
254 kilograms of DMT. Dimethyl p-benzenedicarboxylates, 280 kilogram 1; 4-butyleneglycol, 3.6 kilograms of nanometer titanium dioxide Si catalysts join among the reaction kettle, when reactor temperature reaches 140 ℃, fully stir material, progressively are warmed up to 150 ℃; Gas phase temperature remains on 70 ℃, accomplishes up to permutoid reaction;
(2) esterification amidate action:
After reducing the temperature to 160 ℃ to above-mentioned product of transesterification reaction, add diprotic acid, diamine and nylon 12 homologues, the rising temperature of reaction is at 190 ℃, and the cat head gas phase temperature reacts at 110 ℃, during reaction, feeds rare gas element and is added on protection;
(3) copolycondensation:
Progressively improve temperature of reaction to 260 ℃, carry out progressively to reactive system that extracting air reduces pressure simultaneously, prevent on the material liquid general; After being reacted to 3 hours, set vacuum tightness≤5mmHg, when the product melt flow rate(MFR) reaches 38g/10min; Assert the reaction completion, feed rare gas element, blowing.
Embodiment 2
(1) transesterification reaction:
254g kilogram DMT. Dimethyl p-benzenedicarboxylate, 280 kilogram 1; 4-butyleneglycol, 3.6 kilograms of nanometer titanium dioxide Si catalysts join among the reaction kettle;, fully stirs reactor temperature material when reaching 140 ℃; Progressively be warmed up to 160 ℃, gas phase temperature remains on 75 ℃, accomplishes up to permutoid reaction;
(2) esterification amidate action:
After reducing the temperature to 140 ℃ to above-mentioned product of transesterification reaction, add diprotic acid, diamine and nylon 12 homologues, the rising temperature of reaction is at 180 ℃, and the cat head gas phase temperature reacts at 105 ℃, during reaction, feeds rare gas element and is added on protection;
(3) copolycondensation:
Progressively improve temperature of reaction to 220 ℃, carry out progressively to reactive system that extracting air reduces pressure simultaneously, prevent on the material liquid general; React after 3 hours, set vacuum tightness≤5mmHg, when the product melt flow rate(MFR) reaches 30g/10min; Assert the reaction completion, feed rare gas element, blowing.
Embodiment 3
(1) transesterification reaction:
254g kilogram DMT. Dimethyl p-benzenedicarboxylate, 280 kilogram 1; 4-butyleneglycol, 3.6 kilograms of nanometer titanium dioxide Si catalysts join among the reaction kettle;, fully stirs reactor temperature material when reaching 140 ℃; Progressively be warmed up to 150 ℃, gas phase temperature remains on 70 ℃, accomplishes up to permutoid reaction;
(2) esterification amidate action:
After reducing the temperature to 160 ℃ to above-mentioned product of transesterification reaction, add diprotic acid, diamine and nylon 12 homologues, the rising temperature of reaction is at 190 ℃, and the cat head gas phase temperature reacts at 110 ℃, during reaction, feeds rare gas element and is added on protection;
；
(3) copolycondensation:
Progressively improve temperature of reaction to 220 ℃, carry out progressively to reactive system that extracting air reduces pressure simultaneously, prevent on the material liquid general; React after 3 hours, set vacuum tightness≤5mmHg, when the product melt flow rate(MFR) reaches 30/10min; Assert the reaction completion, feed rare gas element, blowing
Hot melt adhesive in the above embodiment of the present invention and domestic and international related prods are compared, and tabulation as follows
What must understand is that preamble is said only to be further to explain to of the present invention.To those skilled in the art, under the prerequisite that does not deviate from spirit of the present invention, can make different alternativess and improvement.Therefore, present invention includes all alternativess and the conversion scheme thereof that falls into its appended claim scope.
Claims (9)
1. the preparation method of a hot melt adhesive for high-polymer material lining cloth, it is characterized in that: it comprises the steps:
(1) transesterification reaction:
Join raw material DMT. Dimethyl p-benzenedicarboxylate, divalent alcohol, nanometer titanium dioxide Si catalyst among the reaction kettle;, fully stirs reactor temperature material when reaching 140 ℃; Progressively be warmed up to 150～180 ℃, gas phase temperature remains on 60～80 ℃, accomplishes up to permutoid reaction;
(2) esterification amidate action:
After reducing the temperature to 130～150 ℃ to above-mentioned product of transesterification reaction; Add diprotic acid, diamine and nylon 12 homologues, the rising temperature of reaction is at 180～220 ℃, and the cat head gas phase temperature reacts at 100～120 ℃; During reaction, feeding rare gas element protects;
(3) copolycondensation:
Progressively improve temperature of reaction to 240～260 ℃, carry out progressively to reactive system that extracting air reduces pressure simultaneously, vacuum tightness≤5mmHg when the product melt flow rate(MFR) reaches 30-38g/10min, feeds rare gas element, blowing.
2. the preparation method of hot melt adhesive for high-polymer material lining cloth according to claim 1, it is characterized in that: wherein divalent alcohol is 1, the 4-butyleneglycol.
3. the preparation method of hot melt adhesive for high-polymer material lining cloth according to claim 1, it is characterized in that: wherein the particle diameter of nanometer titanium dioxide Si catalyst is less than 10nm.
4. the preparation method of hot melt adhesive for high-polymer material lining cloth according to claim 1, it is characterized in that: wherein the mol ratio of DMT. Dimethyl p-benzenedicarboxylate in the step 1 and divalent alcohol is 1: 1.2.
5. the preparation method of hot melt adhesive for high-polymer material lining cloth according to claim 1, it is characterized in that: wherein diamine is selected from one or more in nonamethylene diamine, decamethylene diamine, the dodecyl diamine.
6. the preparation method of hot melt adhesive for high-polymer material lining cloth according to claim 1, it is characterized in that: wherein diprotic acid is selected from one or more in sebacic acid, SL-AH, tridecanyldicarboxylic acid, 15 carbon dicarboxylic acids, 17 carbon dicarboxylic acids.
7. the preparation method of hot melt adhesive for high-polymer material lining cloth according to claim 1; It is characterized in that: wherein the mol ratio of DMT. Dimethyl p-benzenedicarboxylate and diamine is 1: 0.1-1: 0.3; The mol ratio of terephthalate and nylon 12 homologues is 1: 0.001-1: 0.01, and the mol ratio of terephthalate and diprotic acid is 1: 0.1-1: 0.3.
8. the preparation method of hot melt adhesive for high-polymer material lining cloth according to claim 1, it is characterized in that: wherein the additional proportion of nanometer titanium dioxide Si catalyst is the 0.02wt% of material gross weight.
9. the preparation method of hot melt adhesive for high-polymer material lining cloth according to claim 1, it is characterized in that: wherein pressure range is 0.3MPa-0.05MPa in the step 2.
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| CN101570678B true CN101570678B (en) | 2012-01-04 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935513B (en) * | 2010-09-08 | 2012-03-21 | 上海天洋热熔胶有限公司 | Polyesteramide hot melt adhesive with low melting point and preparation method thereof |
| CN103952114B (en) * | 2014-05-15 | 2016-03-30 | 天津冯德亦康新材料科技有限公司 | A kind of fabrication polyamide binder |
| CN103937440B (en) * | 2014-05-15 | 2016-03-30 | 天津冯德亦康新材料科技有限公司 | A kind of preparation method of fabrication polyamide binder |
| CN104130744A (en) * | 2014-06-19 | 2014-11-05 | 上海天洋热熔粘接材料股份有限公司 | Preparation method of amino-terminated polyester amide hot-melt glue for clothing |
| CN107841280A (en) * | 2016-09-21 | 2018-03-27 | 东莞市舜天实业有限公司 | Polyester micelle |
| CN111518510B (en) * | 2020-04-23 | 2021-10-26 | 浙江恒澜科技有限公司 | Preparation method of long-carbon-chain polyesteramide hot melt adhesive containing side hydrocarbon groups |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4604449A (en) * | 1985-10-09 | 1986-08-05 | Eastman Kodak Company | Process for preparing poly(ester-amides) |
| EP0835896A1 (en) * | 1996-04-30 | 1998-04-15 | Toray Industries, Inc. | Polyester amide copolymer and process for the production thereof, polyester amide monomer and process for the production thereof, and polyester amide resin composition |
| CN1366011A (en) * | 2001-01-18 | 2002-08-28 | 李蹘亨 | Polyamide-polyesteramide thermosol and its preparing process |
-
2009
- 2009-06-04 CN CN2009100993780A patent/CN101570678B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4604449A (en) * | 1985-10-09 | 1986-08-05 | Eastman Kodak Company | Process for preparing poly(ester-amides) |
| EP0835896A1 (en) * | 1996-04-30 | 1998-04-15 | Toray Industries, Inc. | Polyester amide copolymer and process for the production thereof, polyester amide monomer and process for the production thereof, and polyester amide resin composition |
| CN1366011A (en) * | 2001-01-18 | 2002-08-28 | 李蹘亨 | Polyamide-polyesteramide thermosol and its preparing process |
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