CN101092548B - Hot-melt adhesive of thermal shrinkage polyester amide in use for material of thermal shrinkage, and preparation method - Google Patents
Hot-melt adhesive of thermal shrinkage polyester amide in use for material of thermal shrinkage, and preparation method Download PDFInfo
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- CN101092548B CN101092548B CN2007100248844A CN200710024884A CN101092548B CN 101092548 B CN101092548 B CN 101092548B CN 2007100248844 A CN2007100248844 A CN 2007100248844A CN 200710024884 A CN200710024884 A CN 200710024884A CN 101092548 B CN101092548 B CN 101092548B
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- polyester
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- melt adhesive
- thermal shrinkage
- alcoholysis
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Abstract
This invention relates to a polyesteramide hot-melt adhesive for pyrocondensation material, and its preparation method from polyamide and water PET. The polyesteramide hot-melt adhesive has a repeating structure shown in this invention, wherein, R1 is residue derived from dimmer acid; R2 is -(CH2)2-12- and its possible branched isomer; R3 is terephthalate polyester segment (derived from polyesterresidue), terephthalate oligomer, terephthalate dimmer or benzene ring. The preparation method comprises ester-amide exchange, alcoholysis and polycondensation. By utilizing waste polyester as part of the the raw material, the product cost is reduced without sacrificing product quality, and meanwhile white pollution is reduced. The preparation method does not need solvent recovery or product purification, and has such advantages as no pollution, and simple and stable process.
Description
Technical field
The present invention relates to a kind of hot-melt adhesive of thermal shrinkage polyester amide in use for material of thermal shrinkage, and use Versamid and PET polyethylene terephthalate copolymer to prepare the method for hot melt adhesive.
Background technology
Material contracting with heat is the one type of novel material with memory that grows up over nearly 30 years; It is the revolution on the new material development history; Corresponding pyrocondensation goods are applied to power industry, electronic industry, telecommunication industry, automotive industry, war industry and the Family Day of handling official business and use etc.; Have huge application market, along with science and expanding economy, its market potential is unlimited.Pyrocondensation goods still application process itself all need corresponding supporting special-purpose mastic sealant, in the process of material contracting with heat heat shrink, play effects such as bonding, sealing, insulation.Because the inherent excellent properties of polyamide-based hot melt adhesive own makes it can satisfy above application, becomes a kind of high value added product.
The present domestic industrial polyamide-based resin that also is not applicable to these fields.Currently available products is most of for being used for high viscosity, the high softening point resin of clothes.And domestic mass-produced dimeracid low molecule pa resin, softening temperature, viscosity are too low again, and room temperature is fragility, can not satisfy request for utilization.
Have and carry out binary or multi-component copolymer by aromatic diacid and aromatic series or aliphatie diamine usually than high softening-point and polymeric amide hotmelt with better flowability and get.Like USP 5,089,588 and 6,590,063 all to adopt with the phenyl be the polymeric amide of primary structure.In above-mentioned patent, contain many inflexible benzene ring structures in the polymer molecule, make the snappiness of product reduce.In addition, generally adopt solvent polymeric in these methods, can bring problems such as product purification, solvent recuperation in the production, also can cause certain environmental pollution simultaneously.
Through polymeric amide and PET polyester are carried out ester-amide exchange reaction, can generate polyesteramide type segmented copolymer, on polyamide chains, introduce phenyl ring.Pillon L Z, Utracki L A, Pillon D W, Li Ruixia etc. have all reported ester-amide exchange reaction.But their research mainly is to investigate the influence of ester-amide exchange reaction to the physical blending system of nylon polymeric amide and PET polyester.
Through grafting with crosslinkedly carry out modification and prepare polyamide hot, with useless polyester material as partial raw, products therefrom has following structure to Chinese patent 200510098618.7 in the reaction process with a kind of Versamid:
In synthetic, adopt grafting, crosslinked scheme, add expensive grafting agent in the reaction process, product cost is increased, and the technology relative complex.
Summary of the invention
To the above-mentioned defective and the deficiency that exist in the prior art, the problem that the present invention will solve is the stopping reaction condition, realizes softening temperature and viscosity adjustable, reduces material cost, simplifies production technique.The inventive method adopts useless polyester (discarded carafe; As: carafes such as Finda, cola, mineral water) or the Bottle grade Polyester Chips waste material as part material; Not reducing under the product quality premise, both reduced cost, for solving white pollution a kind of new way is provided again.Polyester amide hot melt adhesive according to the present invention has following main repeat unit structure:
R wherein
1, R
2And R
3The following definition:
R wherein
1For being derived from the residue of dimeracid, residue is meant and does not comprise carboxyl, R
2For-(CH
2)
2-12-, R
3For being derived from divalent alcohol, polyether Glycols, polyester diol or the residue of polyol that molecular weight is 28-2000 or being derived from the residue of polyester, said polyester is discarded carafe or Bottle grade Polyester Chips waste material.Certainly, also possibly contain the sub product of other structures in this hot melt adhesive, these sub products are mixed in the product and need not separate, and can not influence product performance, improve toughness of products on the contrary.
In polyester amide hot melt adhesive of the present invention, R
1The residue that is derived from dimeracid of representative comprises the residue that is derived from dimerization oleic acid or linoleic acid dimer etc.
In polyester amide hot melt adhesive of the present invention, R
2Be preferably-(CH
2)
2-,-(CH
2)
3-,-(CH
2)
4-,-(CH
2)
5-,-(CH
2)
6-,-(CH
2)
7-,-(CH
2)
8-,-(CH
2)
9-,-(CH
2)
10-,-(CH
2)
11-,-(CH
2)
12-and various possible branched isomer, more preferably-(CH
2)
4-,-(CH
2)
5-,-(CH
2)
6-,-(CH
2)
7-,-(CH
2)
10-,-(CH
2)
12-and various possible branched isomer, most preferably-(CH
2)
2-6-.
In polyester amide hot melt adhesive of the present invention, R
3Being preferably and being derived from the polyester residue is terephthalate polyester segment, terephthalate oligomer, terephthalate dimer, phenyl ring etc.; More preferably be derived from terephthalate polyester segment, the terephthalate oligomer of useless polyester residue, most preferably be derived from polyester residue terephthalate oligomer.
In polyester amide hot melt adhesive of the present invention, be derived from polyester residue R
3The terephthalate polyester segment in divalent alcohol or polyvalent alcohol, be preferably and be derived from the C that molecular weight is 28-2000
2-C
12Divalent alcohol, polyether Glycols, polyester diol or residue of polyol; More preferably be derived from terepthaloyl moietie, 1; Ammediol, 1,4-butyleneglycol, molecular weight are no more than 2000 the polyoxyethylene glycol or the residue of W 166 or refined caster oil, most preferably are derived from the residue that mixes alcohol.
In the preparation method of polyester amide hot melt adhesive of the present invention, a total three-step reaction is respectively ester-acid amide exchange, alcoholysis, polycondensation.
Building-up process is following: with in Versamid and the reaction kettle of useless polyester in required ratio adding band vacuum and condenser system, stirring heats up down carries out ester-amide exchange reaction, gets segmented copolymer earlier; Add divalent alcohol or polyol reaction number hour in required ratio again, carry out alcoholysis reaction, vacuumize polycondensation again, polyester amide hot melt adhesive.The concrete reactions step of this three-step approach is following:
The first step: Versamid+useless polyester ester-acid amide exchange blend
Second step: blend+divalent alcohol alcoholysis alcoholysis product
The 3rd step: the alcoholysis product polycondensation polyester amide hot melt adhesive of finding time
Being fit to Versamid of the present invention is homemade 010 resin or 011 resin; Used useless polyester is depleted carafe such as Coke bottle, Sprite bottle etc., also can use bottle level polyester tankage; Used alcoholysis reagent is divalent alcohol, polyvalent alcohol, polyether glycol or polyester glycol; Its molecular weight is 28～2000; The example has terepthaloyl moietie, 1, ammediol, 1,2-Ucar 35,1; 4-butyleneglycol, 1,3 butylene glycol, polyoxyethylene glycol, W 166, based on the polyester glycol of hexanodioic acid and terepthaloyl moietie; Wherein can use single alcohol also can use blended alcohol; Its raw material ratio is: Versamid: useless polyester: divalent alcohol=100:1～40:1～20 (w%), and synthesis condition is: vacuum tightness 0.05～0.1MPa; 200～290 ℃ of temperature of reaction; Per 1～6 hour reaction times in step.
According to different request for utilizations, in building-up process,, regulate the product softening temperature through changing blend time, blending temperature; Change dosage, alcoholysis time or the polycondensation time of alcohol, regulate product viscosity.
Advantage of the present invention is to adopt useless polyester (discarded carafe is like carafes such as Finda, cola, mineral waters) as part material, not reducing under the product quality premise, has both reduced cost, and for solving white pollution a kind of new way is provided again.In addition, the present invention adopts mass polymerization, synthesizes through ester-acid amide exchange, alcoholysis, polycondensation, and is pollution-free in the production, avoided solvent recuperation and product to purify, and technology is simple, stable.Raw material adopts homemade 010 resin or 011 resin cost is low, the source abundant.Through changing dosage, alcoholysis time or the polycondensation time etc. of processing condition such as blend time, blending temperature, alcohol, regulate product softening temperature and viscosity.Through the regularity of ester-acid amide exchange, alcoholysis, polycondensation reduction product, reduce the chance that forms hydrogen bond in synthetic, improved the product snappiness.The present invention through method for preparing and polyester amide hot melt adhesive, be used for the bonding of cable heat-shrinkable T bush, have excellent use properties, test result is following:
| Performance test | Test conditions | Performance requriements | TP | Test-results |
| Stripping strength | Air pressure maintenance type (60 ± 2) ℃ non-air pressure maintenance type (23 ± 3) ℃ velocity of separation 50mm/min | To PE sheath >=120N/25mm to plumbous, steel sheath >=100N/25mm | YD/T590 | 346N |
| Shearing resistance | Air pressure maintenance type (60 ± 2) ℃ non-air pressure maintenance type (23 ± 3) ℃ velocity of separation 50mm/min | ≥200N | YD/T590 ? | 362N |
| Environmental stress cracking | Hot melt adhesive is cracking agent (50 ± 2) ℃, 48h | The sheath sample does not ftracture | GB/T1842 | Do not ftracture |
| Corrosive nature to copper, aluminium, steel | Test temperature: (120 ± 2) ℃ hold-time: 16h | No corrosive nature | GB/T7326 | There is not corrosion |
| Water regain | In (23 ± 3) ℃ water, 48h | ≤1.0％ | GB/T1034 | 0.5％ |
Embodiment
The following example is used to explain the present invention, but does not certainly limit the scope of the invention.
The Versamid that in the following example, uses is homemade 010 resin or 011 resin.
Embodiment 1:
Versamid 584g (commodity are called 011 resin, Zhejiang Pujiang resin processing plant, softening temperature is 90～120 ℃) is mixed with useless polyester 58g; Add in the reaction kettle of band vacuum and condenser system, be warming up to material melting, continue to be warming up to 250 ℃ under stirring; Blend 1.5 hours adds terepthaloyl moietie 50g afterwards, alcoholysis 0.5 hour; The polycondensation 1.5 hours of reducing pressure at last, vacuum tightness 0.065MPa.Products obtained therefrom is amber viscous fluid, and the cooling back is the toughness solid, and softening temperature is 166 ℃, and viscosity (190 ℃) is 6000mPaS.Its structural formula is following:
Wherein: R
1Residue for dimeracid; R
2For-(CH
2)
3-; R
3Ethylene glycol terephthalate oligomer for useless polyester residue.
Embodiment 2:
Versamid 584g (commodity are called 010 resin, Yong Lin oil chemistry factory, softening temperature is 90～120 ℃) is mixed with useless polyester 30g; Add in the reaction kettle of band vacuum and condenser system, be warming up to material melting, continue to be warming up to 250 ℃ under stirring; Blend 1.5 hours adds 1,3 butylene glycol 72g afterwards; Alcoholysis 0.5 hour, the polycondensation 1.5 hours of reducing pressure at last, vacuum tightness 0.065MPa.Products obtained therefrom is amber viscous fluid, and the cooling back is the toughness solid.Its structural formula is following:
Wherein: R
1Residue for dimeracid; R
2For-(CH
2)
2-, R
3Ethylene glycol terephthalate and terephthalic acid 1,3 butylene glycol ester oligomer for useless polyester residue.
Embodiment 3:
Versamid 584g (commodity are called 010 resin, Zhejiang Pujiang resin processing plant, softening temperature is 90～120 ℃) is mixed with useless polyester 58g; Add in the reaction kettle of band vacuum and condenser system, be warming up to material melting, continue to be warming up to 250 ℃ under stirring; Blend 1.5 hours adds terepthaloyl moietie 15g, 1 afterwards, 6-pinakon 35g; Alcoholysis 0.5 hour, the polycondensation 1.5 hours of reducing pressure at last, vacuum tightness 0.065MPa.Products obtained therefrom is amber viscous fluid, and the cooling back is the toughness solid.Its structural formula is following:
Wherein: R
1Residue for dimeracid; R
2For-(CH
2)
2-, R
3Be the ethylene glycol terephthalate and the terephthalic acid 1 of useless polyester residue, 6-pinakon ester oligomer.
Embodiment 4:
According to the proportioning of embodiment 1, the blend time is adjusted to 0.5 hour, other conditions are constant.
Embodiment 5:
According to the proportioning of embodiment 1, change the polycondensation time into 1 hour, other conditions are constant.
Comparative Examples:
Versamid 584g (commodity are called 010 resin, Zhejiang Pujiang resin processing plant, softening temperature is 90～120 ℃) is mixed with hexanodioic acid 88g; Sneak into useless polyester again, its add-on is 10% of a polymeric amide weight, adds in the reaction kettle of band vacuum and condenser system; Be warming up to material melting, continue to be warming up to 250 ℃ under stirring, reacted 1 hour; Vacuumized vacuum tightness 0.08MPa then 1 hour.Be cooled to 160 ℃ after stopping to find time, and add terepthaloyl moietie 50g, be warming up to 250 ℃ of reactions 3 hours gradually, vacuumized again 1 hour.Products obtained therefrom is amber viscous fluid, and the cooling back is the toughness solid.
The performance of the foregoing description products obtained therefrom is listed in the table below:
| Embodiment | Softening temperature ℃ | Viscosity mPaS/190 ℃ | 5 ℃ of low-temperature flexibilities, doubling 200 times |
| 1 | 166 | 6000 | Not crooked fractureing |
| 2 | 141 | 3600 | Not crooked fractureing |
| 3 | 160 | 5300 | Not crooked fractureing |
| 4 | 115 | 5600 | Not crooked fractureing |
| 5 | 165 | 4000 | Not crooked fractureing |
| Comparative Examples | 160 | 3000 | Not crooked fractureing |
Claims (1)
1. the preparation method of a hot-melt adhesive of thermal shrinkage polyester amide in use for material of thermal shrinkage; It comprises ester-acid amide exchange, alcoholysis, polycondensation three-step reaction; It is characterized in that: add Versamid and polyester in the reaction kettle of band vacuum and condenser system in required ratio earlier; Stirring heats up down carries out ester-amide exchange reaction, gets segmented copolymer; Add divalent alcohol or polyol reaction in required ratio again, carry out alcoholysis reaction, vacuumize polycondensation again, get polyester amide hot melt adhesive; Used Versamid is homemade 011 resin; Useless polyester is discarded carafe or Bottle grade Polyester Chips waste material; Used alcoholysis reagent is that single alcohol also can be used blended alcohol, and its molecular weight is 28～2000; Its raw material weight ratio is: Versamid: useless polyester: divalent alcohol=100: 1～40: 1～20, and synthesis condition is: vacuum tightness 0.05～0.1MPa; 200～290 ℃ of temperature of reaction; Per 1～6 hour reaction times in step.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100248844A CN101092548B (en) | 2007-07-05 | 2007-07-05 | Hot-melt adhesive of thermal shrinkage polyester amide in use for material of thermal shrinkage, and preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100248844A CN101092548B (en) | 2007-07-05 | 2007-07-05 | Hot-melt adhesive of thermal shrinkage polyester amide in use for material of thermal shrinkage, and preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN101092548A CN101092548A (en) | 2007-12-26 |
| CN101092548B true CN101092548B (en) | 2012-01-18 |
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| CN102372922B (en) * | 2010-08-18 | 2014-09-10 | 上海杰事杰新材料(集团)股份有限公司 | Polyesteramide multi-block copolymer and preparation method thereof |
| CN102382614A (en) * | 2011-09-13 | 2012-03-21 | 烟台德邦电子材料有限公司 | Polyamide hot melt adhesive for adhering nonpolar materials and preparation method thereof |
| CN107841280A (en) * | 2016-09-21 | 2018-03-27 | 东莞市舜天实业有限公司 | Polyester micelle |
| CN112920436B (en) * | 2021-01-26 | 2022-05-20 | 安徽农业大学 | Application of polyesteramide as high-temperature-resistant heat-shrinkable film |
| CN113185943B (en) * | 2021-04-15 | 2022-12-20 | 上海抚佳精细化工有限公司 | Polyurethane hot melt adhesive and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1366011A (en) * | 2001-01-18 | 2002-08-28 | 李蹘亨 | Polyamide-polyesteramide thermosol and its preparing process |
| WO2005092963A1 (en) * | 2004-03-26 | 2005-10-06 | Do Gyun Kim | Recycled method for a wasted polymer which is mixed polyester polyamide and reclaimed materials thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1366011A (en) * | 2001-01-18 | 2002-08-28 | 李蹘亨 | Polyamide-polyesteramide thermosol and its preparing process |
| WO2005092963A1 (en) * | 2004-03-26 | 2005-10-06 | Do Gyun Kim | Recycled method for a wasted polymer which is mixed polyester polyamide and reclaimed materials thereof |
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| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Changzhou Baoli Adhesive Co., Ltd. Assignor: Jiangsu Polytechnic University Contract record no.: 2012320000522 Denomination of invention: Hot-melt adhesive of thermal shrinkage polyester amide in use for material of thermal shrinkage, and preparation method Granted publication date: 20120118 License type: Exclusive License Open date: 20071226 Record date: 20120424 |
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Address after: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee after: Jiangsu Polytechnic University Address before: 213016 Baiyun Road, Jiangsu, Changzhou Patentee before: Jiangsu Polytechnic University |
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