CN102559127A - High temperature resistant hot melt adhesive and processing process thereof - Google Patents
High temperature resistant hot melt adhesive and processing process thereof Download PDFInfo
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- CN102559127A CN102559127A CN2010105944779A CN201010594477A CN102559127A CN 102559127 A CN102559127 A CN 102559127A CN 2010105944779 A CN2010105944779 A CN 2010105944779A CN 201010594477 A CN201010594477 A CN 201010594477A CN 102559127 A CN102559127 A CN 102559127A
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Abstract
The invention provides a formula of a high temperature resistant hot melt adhesive and a processing process of the hot melt adhesive. The formula comprises the following components: polyamide, an ethylene-ethyl acrylate copolymer, an ethylene-vinyl acetate copolymer, a tackifier, an antioxidant and a modifier. The high temperature resistant hot melt adhesive is high in bonding strength, resistant to high temperature, excellent in insulating and sealing performance, resistant to a low temperature, environment-friendly, non-toxic, simple in production process and good in repeatability.
Description
Technical field
The present invention relates to chemical material technical field, particularly a kind of agglutinating High-temp.-resistant hot-melt adhesive and complete processing thereof that is specially adapted to heat-shrinkage materials (PE, PP, PVC) such as telecommunication cable plastic heat-shrinkable sleeve and petroleum casing pipe.
Background technology
Laying of communication cable, power cable, optical cable; Form various terminal. need butt junction to connect and protect: oil and gas pipes needs coating in anticorrosion, the insulation of tube and tube interface; Coating material and mode are different, but most convenient. and the coating mode of widespread use is to adopt the heat shrinkable sleeve pipe.
Heat-shrinkage material is claimed polymer shape memory material again.What no matter be material contracting with heat itself or its application process to hot melt adhesive all has a higher requirement.At first, heat-shrinkage material needs when using heat to reach the purpose of contraction material, especially during outdoor study; Because working conditions restriction; The workmen is many to heat heat-shrinkable T bush with firelock, and the local heating temperature is higher, and this has just proposed higher requirement to the temperature tolerance of hot melt adhesive.Continuing mainly of heat-shrinkable T bush and joint realized bonding and sealing by hot melt adhesive in addition, especially more need use high-quality hot melt adhesive bonding for the joint sealing of air pressure maintenance type.Traditional EVA class blend hot melt adhesive, this type glue resistance toheat is relatively poor, can leak gas because of the serious decline of bonding strength in high hot weather or more than 60 ℃, can only require lower place to use.What use at present mainly is the thermotolerance polyamide-based hot melt adhesive of dimer acid type preferably.
It is the polymeric amide of primary structure that USP 5089588 adopts with the phenyl, employing be solvent polymeric, have product to purify and the solvent recuperation problem in the production, and can cause certain environmental pollution.Chinese patent 200710024884.4 has adopted the method for Versamid and polyethylene terephthalate copolymerization to invent the special-purpose hot melt adhesive of a kind of material contracting with heat, and synthetic hot melt adhesive temperature tolerance is better.What this invention was adopted is mass polymerization, makes through ester-acid amide exchange, alcoholysis, polycondensation three-step reaction, and production technique is comparatively complicated.
Summary of the invention
The present invention provides that a kind of cohesive strength is high, high temperature resistant, insulated enclosure excellent performance, low temperature resistant and environment-protecting asepsis, production technique is simple and the High-temp.-resistant hot-melt adhesive and the complete processing thereof of good reproducibility.
To achieve these goals, the present invention provides following technical scheme:
A kind of prescription of High-temp.-resistant hot-melt adhesive, it comprises following component according to ratio of weight and number:
Polymeric amide 20-70
Ethylene ethyl acrylate copolymer 0-40
EVAc 20-40
Tackifier 5-30
Oxidation inhibitor 0.5-3
Properties-correcting agent 0.5-2.
Preferably, said polymeric amide is a dimer acid type polyamide, comprises homopolyamide and copolyamide; Said polymeric amide diamines and di-carboxylic acid repeat units derived constitute, and are perhaps made by the lactan ring-opening polymerization, wherein; Said diamines comprises aliphatie diamine, alicyclic diamine or aromatic diamine; Said di-carboxylic acid comprises aliphatic dicarboxylic acid, alicyclic di-carboxylic acid or aromatics unit carboxylic acid, and said lactan contains 5-12 carbon atom, and the fusing point of said polymeric amide is 100 ℃-160 ℃.
Preferably, said lactan contains 6-8 carbon atom, and the fusing point of said polymeric amide is 120 ℃-150 ℃.
Preferably, the content of the ethyl propenoate of said ethylene ethyl acrylate copolymer (EA) is that 5-50% (according to weight percent), melting index are 1-40.0g/10min.
Preferably, the ethyl propenoate content of said ethylene ethyl acrylate copolymer is that 20-40% (according to weight percent), melting index are 20-30g/10min.
Preferably, the vinyl acetate content of said EVAc is 10-60% (according to weight percent), melting index 5-450g/10min.
Preferably, the vinyl acetate content of said EVAc is that 20-40% (according to weight percent), melting index are 10-200g/10min.
Preferably, said tackifier are one or several mixture of terpine resin, petroleum resin and verivate thereof.Said oxidation inhibitor is composite antioxidant, comprising: four (β-(3, three grades of butyl of 5--4-hydroxy phenyl) propionic acid) pentaerythritol ester, N, N '-two-[3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl group] hexanediamine and thio-2 acid two octadecyl esters.These three kinds of materials can mix by arbitrary proportion.
Preferably, said properties-correcting agent is flow ability modifying agent, comprising: wax, said wax are paraffin, polyethylene wax or Microcrystalline Wax.
The present invention also provides a kind of complete processing of High-temp.-resistant hot-melt adhesive, and it comprises step:
The preparation steps of A, material:, take by weighing the material of each component according to the described prescription of technique scheme;
B, premix step:, can carry out the banburying granulation earlier for difficult fused polymeric amide and ethylene ethyl acrylate copolymer;
C, mixing step: adopt twin screw extruder to carry out the material of above-mentioned each component mixing;
D, granulation step: the method that adopts the pelletizing of recirculated water cooling hobboing cutter is carried out granulation with above-mentioned material after mixing;
E, packing and storing step: packing box obtains required hot melt adhesive after storing said granulation.
Through implementing above technical scheme; Has following technique effect: High-temp.-resistant hot-melt adhesive provided by the invention and complete processing thereof; It can resistant to elevated temperatures polymeric amide be material of main part that this hot melt adhesive adopts, and maximum operation (service) temperature can reach 140 ℃, can satisfy the requirement of heat-shrink tube to temperature; And in the use, can not cause the reduction of cohesive strength because of the rising of envrionment temperature.Applicable to multiple severe environment.
This hot melt adhesive can effectively bond to Vilaterm (PE), Vestolen PP 7052 (PP) and SE (PVC), and cohesive strength is higher, and is good with external wall material bonding back insulated enclosure property.
Added fabulous ethylene ethyl acrylate copolymer (EEA) and the EVAc (EVA) of resistance to low temperature in this thermosol formula, can anti--40 ℃ low temperature, cohesive strength no change under low temperature environment does not have the embrittlement phenomenon yet
This hot melt adhesive (ROHS) detects through " some objectionable impurities instruction is used in restriction in the electronic electric equipment " of European Union's promulgation, human body and environment are not all had harm, and no obnoxious flavour produces in the use.
This hot melt adhesive production technique is simple, employing be the blend preparation technology of simple actual effect, avoided solvent recuperation and purification of products, the technology simple and stable, good reproducibility, thus guaranteed quality product.No obnoxious flavour produces in the production process, and environment is not had harm.Production energy consumption is lower, has better economic effect and suitability for industrialized production prospect.Be specially adapted to the connection and the protection of communication cable, power cable, oil and gas pipes joint.The performance index of hot melt adhesive of the present invention are as shown in table 1 below:
Table 1:
Embodiment
Technical scheme is for a better understanding of the present invention described embodiment provided by the invention below in detail.
The embodiment of the invention provides a kind of High-temp.-resistant hot-melt adhesive prescription, according to ratio of weight and number, comprises following
Component:
Polyamide (PA) 20-70
Ethylene ethyl acrylate copolymer (EEA) 0-40
EVAc (EVA) 20-40
Tackifier 5-30
Oxidation inhibitor 0.5-3
Properties-correcting agent 0.5-2.
Wherein, said polymeric amide is a dimer acid type polyamide, comprises homopolyamide and copolyamide; Said polymeric amide diamines and di-carboxylic acid repeat units derived constitute, and are perhaps made by the lactan ring-opening polymerization, wherein; Said diamines comprises aliphatie diamine, alicyclic diamine or aromatic diamine; Said di-carboxylic acid comprises aliphatic dicarboxylic acid, alicyclic di-carboxylic acid or aromatics unit carboxylic acid, and said lactan contains 5-12 carbon atom, and the fusing point of said polymeric amide is 100 ℃-160 ℃.Preferably, said lactan contains 6-8 carbon atom, and the fusing point of said polymeric amide is 120 ℃-150 ℃.
Wherein, the content of the ethyl propenoate of said ethylene ethyl acrylate copolymer (EA) is that 5-50% (according to weight percent), melting index are 1-40.0g/10min.Preferably, the content of the ethyl propenoate of said ethylene ethyl acrylate copolymer (EA) is that 5-50% (according to weight percent) is 20-30g/10min for 20-40% (according to weight percent), melting index.
Wherein, vinyl acetate (VA) content of said EVAc (EVA) is 10-60% (according to weight percent), melting index 5-450g/10min.Preferably, vinyl acetate (VA) content of said EVAc (EVA) is that 20-40% (according to weight percent), melting index are 10-200g/10min.The used EVA of the present invention is the mixing of the multiple trade mark that meets the demands.
Wherein, said tackifier are one or several mixture of terpine resin, petroleum resin and verivate thereof.Said oxidation inhibitor is composite antioxidant, comprising: four (β-(3, three grades of butyl of 5--4-hydroxy phenyl) propionic acid) pentaerythritol ester, N, N '-two-[3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl group] hexanediamine and thio-2 acid two octadecyl esters.These three kinds of materials can mix by arbitrary proportion.
Wherein, said properties-correcting agent is flow ability modifying agent, comprising: wax, said wax are paraffin, polyethylene wax or Microcrystalline Wax.
Embodiment one: HMP dimer acid type polyamide resin (156 ℃ of softening temperatures) 40g, ethylene vinyl acetate (EVA210) 20g, ethylene vinyl acetate (EVA150) 10g, ethylene vinyl acetate (EVA930) 10g, terpine resin, antioxidant 1010 1g, oxidation inhibitor 10981g, oxidation inhibitor 8020.5g, polyethylene wax 0.5g; Carry out mixing in the adding twin screw extruder; Melting temperature is 120 ℃; Mixing twice; Adopt the pelletizing of recirculated water cooling hobboing cutter to make the high-melting point polyamide thermosol product, 142 ℃ of the softening temperature positions of this product, viscosity is 144000mpa.s.
Embodiment two: HMP dimer acid type polyamide resin (156 ℃ of softening temperatures) 35g, ethylene ethyl acrylate (EEA) 15g, ethylene vinyl acetate (EVA930) 10g, terpine resin 30g, ethylene vinyl acetate (EVA210) 7g, antioxidant 1010 1g, oxidation inhibitor 10981g, oxidation inhibitor 8020.5g, polyethylene wax 0.5g; PA150 and EEA897 carry out mixing in Banbury mixer earlier; Carry out mixing in all subsequently material adding twin screw extruders; Melting temperature is 120 ℃, and is mixing twice, adopts the pelletizing of recirculated water cooling hobboing cutter to make the high-melting point polyamide thermosol product; 145 ℃ of the softening temperature positions of this product, viscosity are 154000mpa.s.
Embodiment three: HMP dimer acid type polyamide resin (146 ℃ of softening temperatures) 50g, ethylene vinyl acetate (trade(brand)name EVA220; Available from Mitsui company) 20g, ethylene vinyl acetate (EVA150;) 10g, terpine resin 17g, antioxidant 1010 1g, oxidation inhibitor 10981g, oxidation inhibitor 8020.5g, polyethylene wax 0.5g, adding and carry out mixingly in the twin screw extruder, melting temperature is 120 ℃; Mixing twice; Adopt the pelletizing of recirculated water cooling hobboing cutter to make the high-melting point polyamide thermosol product, 149 ℃ of the softening temperature positions of this product, viscosity is 156000mpa.s.
The embodiment of the invention also provides a kind of complete processing of High-temp.-resistant hot-melt adhesive, and it comprises step:
The preparation steps of A, material:, take by weighing the material of each component according to the described prescription of above-mentioned each embodiment;
B, premix step:, can carry out the banburying granulation earlier for difficult fused polymeric amide and ethylene ethyl acrylate copolymer;
C, mixing step: it is mixing to adopt material that twin screw extruder will above-mentioned each component to carry out, and utilizes the shearing force greatly of twin screw extruder to make material fully mixing.The material that configures carries out mixing under 100 ℃-140 ℃.For guaranteeing mixing homogeneity, answer mixing 2 to 3 times.
D, granulation step: the method that adopts the pelletizing of recirculated water cooling hobboing cutter is carried out granulation with above-mentioned material after mixing; Make the particle diameter of this hot melt adhesive micelle even, be beneficial to blanking.
E, packing and storing step: packing box obtains required hot melt adhesive after storing said granulation.Because the hot melt adhesive that makes is easy to suction, should seal preservation.
More than a kind of High-temp.-resistant hot-melt adhesive prescription and complete processing thereof that the embodiment of the invention provided have been carried out detailed introduction; For one of ordinary skill in the art; Thought according to the embodiment of the invention; The part that on embodiment and range of application, all can change, in sum, this description should not be construed as limitation of the present invention.
Claims (10)
1. the prescription of a High-temp.-resistant hot-melt adhesive is characterized in that, according to ratio of weight and number, comprises following component:
Polymeric amide 20-70
Ethylene ethyl acrylate copolymer 0-40
EVAc 20-40
Tackifier 5-30
Oxidation inhibitor 0.5-3
Properties-correcting agent 0.5-2.
2. the prescription of High-temp.-resistant hot-melt adhesive according to claim 1 is characterized in that said polymeric amide is a dimer acid type polyamide; Comprise homopolyamide and copolyamide; Said polymeric amide diamines and di-carboxylic acid repeat units derived constitute, and are perhaps made by the lactan ring-opening polymerization, wherein; Said diamines comprises aliphatie diamine, alicyclic diamine or aromatic diamine; Said di-carboxylic acid comprises aliphatic dicarboxylic acid, alicyclic di-carboxylic acid or aromatics unit carboxylic acid, and said lactan contains 5-12 carbon atom, and the fusing point of said polymeric amide is 100 ℃-160 ℃.
3. like the prescription of the said High-temp.-resistant hot-melt adhesive of claim 2, it is characterized in that said lactan contains 6-8 carbon atom, the fusing point of said polymeric amide is 120 ℃-150 ℃.
4. the prescription of High-temp.-resistant hot-melt adhesive according to claim 1 is characterized in that the content of the ethyl propenoate of said ethylene ethyl acrylate copolymer is that 5-50% (according to weight percent), melting index are 1-40.0g/10min.
5. like the prescription of the said High-temp.-resistant hot-melt adhesive of claim 4, it is characterized in that the ethyl propenoate content of said ethylene ethyl acrylate copolymer is that 20-40% (according to weight percent), melting index are 20-30g/10min.
6. the prescription of High-temp.-resistant hot-melt adhesive according to claim 1 is characterized in that the vinyl acetate content of said EVAc is 10-60% (according to weight percent), melting index 5-450g/10min.
7. like the prescription of the said High-temp.-resistant hot-melt adhesive of claim 6, it is characterized in that the vinyl acetate content of said EVAc is that 20-40% (according to weight percent), melting index are 10-200g/10min.
8. the prescription of High-temp.-resistant hot-melt adhesive according to claim 1; It is characterized in that said tackifier are one or several mixture of terpine resin, petroleum resin and verivate thereof, said oxidation inhibitor is composite antioxidant; Comprise: four (β-(3; Three grades of butyl of 5--4-hydroxy phenyl) propionic acid) pentaerythritol ester, N, N-is two-[3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl group] diamines and thio-2 acid two octadecyl esters totally three kinds of material arbitrary proportion blended mixtures.
9. the prescription of High-temp.-resistant hot-melt adhesive according to claim 1, it is characterized in that said properties-correcting agent is flow ability modifying agent, comprising: wax, said wax are paraffin, polyethylene wax or Microcrystalline Wax.
10. the complete processing of a High-temp.-resistant hot-melt adhesive is characterized in that, comprises step:
The preparation steps of A, material: prescription according to claim 1 takes by weighing the material of each component;
B, premix step:, can carry out the banburying granulation earlier for difficult fused polymeric amide and ethylene ethyl acrylate copolymer;
C, mixing step: adopt twin screw extruder to carry out the material of above-mentioned each component mixing;
D, granulation step: the method that adopts the pelletizing of recirculated water cooling hobboing cutter is carried out granulation with above-mentioned material after mixing;
E, packing and storing step: packing box obtains required hot melt adhesive after storing said granulation.
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| CN2010105944779A CN102559127A (en) | 2010-12-16 | 2010-12-16 | High temperature resistant hot melt adhesive and processing process thereof |
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| CN2010105944779A CN102559127A (en) | 2010-12-16 | 2010-12-16 | High temperature resistant hot melt adhesive and processing process thereof |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232824A (en) * | 2013-04-15 | 2013-08-07 | 中国核电工程有限公司 | Irradiation-resistant hot melt adhesive and preparation method thereof |
| CN103333625A (en) * | 2013-07-01 | 2013-10-02 | 江苏达胜热缩材料有限公司 | Heat-shrinkable composite insulating tape |
| CN104087202A (en) * | 2014-06-26 | 2014-10-08 | 滁州市光威化工有限公司 | Rare earth hot melt adhesive |
| CN104497958A (en) * | 2014-12-09 | 2015-04-08 | 上海海隆石油化工研究所 | Adhesive for corrosion prevention of 3PP pipeline |
| CN104531013A (en) * | 2014-11-26 | 2015-04-22 | 上海邦中高分子材料有限公司 | High-temperature-resistant bonding resin and preparation method thereof |
| CN104804672A (en) * | 2015-04-22 | 2015-07-29 | 深圳市沃尔核材股份有限公司 | Hot melt adhesive for electric cable accessory of nuclear power station |
| CN104804671A (en) * | 2015-04-22 | 2015-07-29 | 深圳市沃尔核材股份有限公司 | Hot melt adhesive inner-layer material of heat-shrinkable tubing for nuclear power station |
| CN105969252A (en) * | 2016-07-01 | 2016-09-28 | 杭州富通通信技术股份有限公司 | Invisible optical cable and self-adhering coating glue |
| CN107312464A (en) * | 2016-08-29 | 2017-11-03 | 上海永韬热熔胶有限公司 | A kind of EVA types PUR and preparation method thereof |
| CN107384296A (en) * | 2017-07-05 | 2017-11-24 | 林立州 | A kind of hot melts agent of photovoltaic film and metal composite |
| CN107501697A (en) * | 2016-06-14 | 2017-12-22 | 上海长园电子材料有限公司 | It is easy to long-term formula of thermal contraction double-walled pipe for storing and transporting and preparation method thereof |
| CN107973972A (en) * | 2017-12-21 | 2018-05-01 | 上海长园电子材料有限公司 | A kind of puncture-resistant thermal contraction double-walled pipe and preparation method thereof |
| CN108690550A (en) * | 2018-05-14 | 2018-10-23 | 启东鑫天鼎热熔胶有限公司 | A kind of formula and preparation method thereof of weaving high temperature resistant water washing polyamide hot-melt adhesive |
| CN110027295A (en) * | 2019-03-21 | 2019-07-19 | 东莞市中鼎塑料制品有限公司 | A kind of manufacturing method of vamp |
| CN111411679A (en) * | 2020-04-22 | 2020-07-14 | 广东天濠建设工程有限公司 | Municipal drainage pipeline construction process |
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| CN1990810A (en) * | 2005-12-30 | 2007-07-04 | 上海轻工业研究所有限公司 | High-melting point polyamide thermosol composition and method of making the same |
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| US5548027A (en) * | 1992-04-03 | 1996-08-20 | Henkel Kommanditgesellschaft Auf Aktien | Hotmelt adhesive |
| CN1222928A (en) * | 1996-06-21 | 1999-07-14 | 阿托芬德利公司 | Hydrophilic hot melt adhesive |
| CN1990810A (en) * | 2005-12-30 | 2007-07-04 | 上海轻工业研究所有限公司 | High-melting point polyamide thermosol composition and method of making the same |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232824B (en) * | 2013-04-15 | 2015-11-04 | 中国核电工程有限公司 | A kind of Irradiation-resistanhot hot melt adhesive and preparation method thereof |
| CN103232824A (en) * | 2013-04-15 | 2013-08-07 | 中国核电工程有限公司 | Irradiation-resistant hot melt adhesive and preparation method thereof |
| CN103333625A (en) * | 2013-07-01 | 2013-10-02 | 江苏达胜热缩材料有限公司 | Heat-shrinkable composite insulating tape |
| CN103333625B (en) * | 2013-07-01 | 2015-02-18 | 江苏达胜热缩材料有限公司 | Heat-shrinkable composite insulating tape |
| CN104087202A (en) * | 2014-06-26 | 2014-10-08 | 滁州市光威化工有限公司 | Rare earth hot melt adhesive |
| CN104087202B (en) * | 2014-06-26 | 2016-03-23 | 滁州市光威化工有限公司 | A kind of rare earth hot melt adhesive |
| CN104531013A (en) * | 2014-11-26 | 2015-04-22 | 上海邦中高分子材料有限公司 | High-temperature-resistant bonding resin and preparation method thereof |
| CN104497958A (en) * | 2014-12-09 | 2015-04-08 | 上海海隆石油化工研究所 | Adhesive for corrosion prevention of 3PP pipeline |
| CN104804671A (en) * | 2015-04-22 | 2015-07-29 | 深圳市沃尔核材股份有限公司 | Hot melt adhesive inner-layer material of heat-shrinkable tubing for nuclear power station |
| CN104804672A (en) * | 2015-04-22 | 2015-07-29 | 深圳市沃尔核材股份有限公司 | Hot melt adhesive for electric cable accessory of nuclear power station |
| CN107501697A (en) * | 2016-06-14 | 2017-12-22 | 上海长园电子材料有限公司 | It is easy to long-term formula of thermal contraction double-walled pipe for storing and transporting and preparation method thereof |
| CN105969252A (en) * | 2016-07-01 | 2016-09-28 | 杭州富通通信技术股份有限公司 | Invisible optical cable and self-adhering coating glue |
| CN107312464A (en) * | 2016-08-29 | 2017-11-03 | 上海永韬热熔胶有限公司 | A kind of EVA types PUR and preparation method thereof |
| CN107384296A (en) * | 2017-07-05 | 2017-11-24 | 林立州 | A kind of hot melts agent of photovoltaic film and metal composite |
| CN107973972A (en) * | 2017-12-21 | 2018-05-01 | 上海长园电子材料有限公司 | A kind of puncture-resistant thermal contraction double-walled pipe and preparation method thereof |
| CN108690550A (en) * | 2018-05-14 | 2018-10-23 | 启东鑫天鼎热熔胶有限公司 | A kind of formula and preparation method thereof of weaving high temperature resistant water washing polyamide hot-melt adhesive |
| CN110027295A (en) * | 2019-03-21 | 2019-07-19 | 东莞市中鼎塑料制品有限公司 | A kind of manufacturing method of vamp |
| CN111411679A (en) * | 2020-04-22 | 2020-07-14 | 广东天濠建设工程有限公司 | Municipal drainage pipeline construction process |
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Application publication date: 20120711 |