CN1121101A - Polyamide hot-melt adhesive and its prepn. method - Google Patents
Polyamide hot-melt adhesive and its prepn. method Download PDFInfo
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- CN1121101A CN1121101A CN94116955A CN94116955A CN1121101A CN 1121101 A CN1121101 A CN 1121101A CN 94116955 A CN94116955 A CN 94116955A CN 94116955 A CN94116955 A CN 94116955A CN 1121101 A CN1121101 A CN 1121101A
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Abstract
The present invention is an improvement of available technology and it includes raw material selection and synthesis process. The present invention uses no aromatic compound and other noxious monomer and solvent, nd it uses fire retardant so as to obtain tenacious fire retardant adhesive with narrow molten range, high softening point and excellent electrical performance.
Description
The invention relates to a kind of polyamide hot and preparation method thereof.
This product generates intermediate product C by the random polyamide resin B reaction that long-chain fat diacid A and dimeracid and short-chain diamine reaction obtain, and intermediate product C gets with the further prepared in reaction of aliphatie diamine D again.
This polyamide hot can be used for being adhesively fixed of electronic devices and components such as televisor deflector coil, the bonding and multiple porous of metallic substance and non-porous material bonding.
Mainly get as the polymeric amide of Hotmelt Adhesive by aromatic diacid and aromatic series and long-chain fat family diamines binary copolymerization or terpolymer.In JP59-126483, the repeating unit of polymeric amide is:
Wherein: R is-(CH
2)
6-12-, Ar is
Among the US 5089588, the polymeric amide repeating unit is:
Wherein: R
1For-(CH
2)
4-10-, R
2Be the alkyl of-OH or 1-4 carbon, R3 is
Ar is
Yet, in crossing a little methods, contain many inflexible benzene ring structures in the molecule of polymkeric substance, make the snappiness of product reduce.In addition, generally use solvent polymeric in these methods, can bring problems such as product separation, solvent recuperation, also can cause certain environmental pollution simultaneously in these methods of industrial enforcement.
The flame retardancy problem that another problem that generally runs into is a product.In the disclosed method of JP 52-146446 this has been done improvement, its method is to sneak into mineral filler such as magnesium hydroxide in the polyamide-based resin of hot-melting type, forms the flame retardancy hotmelt.
The problem that this method exists is that mechanical impurity is brought in the adding of mineral filler sometimes into, as handles badly, can stop up the glue gun sprayer when using tackiness agent, from material solution flame retardancy problem itself.
The objective of the invention is to overcome the above-mentioned weak point of prior art, a kind of flame retardancy hot-melting type polyamide product and bulk polymerization thereof that snappiness is good, softening temperature is high, fusion range is narrow, electrical property is excellent that be intended to obtain is provided.
The random polymeric amide B that the present invention obtains with unsaturated aliphatic dimeracid and short-chain diamine reaction is that basic raw material and the diprotic acid A of long-chain fat family carry out bulk reaction generation intermediate product C, intermediate product C carries out partial cross-linked with aliphatie diamine D again, the toughness and the softening temperature of product both can have been improved, can realize the flame retardancy of product again, can also solve simultaneously the environmental problem in the production, thereby finish the present invention.
The repeating unit of product of the present invention is:
R wherein
1Be dimeracid, R
2, R
4For-(CH
2)
2-12-, R3 is-(CH
2)
6-13-.
In the methods of the invention, the ingredient proportion of B and A reaction is pressed B: A=1: 0.4～1, and in the reaction of intermediate product C and D, the charging capacity of D is the 80%-100% of theoretical value, the calculation formula of its theoretical value is:
In the formula: Wd is the theoretical charging capacity of the anti-family of raw material fat diamines;
Ac is the acid number of intermediate product C;
Wc is the charging capacity of intermediate product C;
Md is the molecular weight of feedstock fat family diamines.
The raw material acid that is fit to the inventive method is C
6-C
36Aliphatics saturated or unsaturated dibasic acid and dimeracid.Amine is C
2-C
12Aliphatie diamine.
In order to remove the water of generation, guarantee to react and carry out smoothly among the present invention, building-up reactions is preferably under the negative pressure carries out, and vacuum tightness is 500-760mmHg, is preferably 700-760mmHg.
In the methods of the invention, raw material is participated in reaction with molten state, and its synthesis reaction temperature is preferably between 150-300 ℃.
Building-up reactions of the present invention is carried out under acidic conditions, carries out fully for guaranteeing reaction, and the reaction times is no less than 4 hours, is preferably 4-10 hour.
In the method for the invention, can react separately, also can mix and react with two or more diprotic acid with a kind of diprotic acid.
Can use separately by products therefrom of the present invention, also two kinds of reaction raw materials products therefroms can be mixed and use.
Hot-melting type polyamide binder softening temperature height of the present invention, fusion range is narrow, and good toughness has good electrical property and good flame retardancy, and does not contain deleterious aromatic seriesization and thing.
Reaction product of the present invention if desired can be further and the composite use of mineral filler, to satisfy different service requirementss, can be used for the bonding of the bonding and multiple porous of bonding, fixing, metallic substance of electronic devices and components such as televisor deflector coil and non-porous material, being specially adapted to some toughness and anti-envrionment temperatures to adhesives requires high, fusion model-enclose requirement is narrow, and electrical property and flame retardancy require harsh occasion.
The invention provides a kind of hot-melting type polyamide product that obtains by bulk polymerization and preparation method thereof.The products obtained therefrom snappiness be improved significantly, softening temperature significantly improves, the flame retardancy of product reaches UL-94 V-0 level.Need not to add solvent in the reaction process, all substances in the system are all participated in reaction, and products obtained therefrom need not separate, and has avoided aftertreatment work such as solvent recuperation, cut down the consumption of energy, and reduce environmental pollution.
The inventive method can be used for synthetic various types of polymeric amide, particularly hot-melting type polymeric amide.
Method of the present invention is simple, and is free from environmental pollution.
Specify product of the present invention and method by the following examples.Embodiment 1
Will be by gathering random polymeric amide B (commodity are called 011 resin, softening temperature 80-130 ℃) and the C that linolic acid and quadrol polycondensation obtain
13Diprotic acid A is by 1.5: 1mol is than mixing, and adds band and vacuumizes in the reactor with condenser system, drips the phosphoric acid of 0.05% (w), under agitation is warming up to 260 ℃, react 4 hours, vacuumize then 1 hour (vacuum tightness is＞700mmHg).Reaction mass is cooled to 200 ℃, stops to find time, add the hexanediamine D of 90% theoretical consumption and 0.05% phosphoric acid, reaction is 1 hour under this temperature, is warming up to 260 ℃ then and reacts 1 hour under the state of vacuumizing.Products obtained therefrom is a red-brown thickness body at night, is cooled to be toughness solid, 154 ℃ of softening temperatures, viscosity (200 ℃) 640mPa.S, acid number 23mgKOH/g after the room temperature.Embodiment 2
Under the operational condition of embodiment 1, with C
13Diprotic acid C
10Diprotic acid replaces.Embodiment 3
Under the operational condition of embodiment 1, with C
13Diprotic acid C
13With C
10Mixture (the mol ratio is 1: 1) replace.Embodiment 4
The product that will obtain respectively under the condition of embodiment 1 and 2 mixed by 1: 4.Embodiment 5
With embodiment 1,2,3,4 product respectively with Al (OH)
3Mix with 3: 2 (w).
The foregoing description products obtained therefrom is listed in table 1.Table 1
| Embodiment | Softening temperature (℃) | Viscosity (200 ℃) | Flame retardancy (UL-94) | Low-temperature performance (5 ℃) | Shearing resistance AL-AL (MPa) |
| ????1 | ????154 | ????640 | ????V-0 | Do not fracture | ????7.1 |
| ????2 | ????156 | ????600 | ????V-0 | Do not fracture | ????6.9 |
| ????3 | ????155 | ????620 | ????V-0 | Do not fracture | ????7.0 |
| ????4 | ????155 | ????620 | ????V-0 | Do not fracture | ????7.0 |
| ????5 | ????157 | ?2.5×10 3 | ????V-0 | Do not fracture | ????9.4 |
Claims (9)
1. polyamide hot is characterized in that having following repeat unit structure:
R wherein
1Be dimeracid, R
2, R
4For-(CH
2)-
2-12, R
3For-(CH
2)-
8-13
2. the synthetic method of a hot melt adhesive as claimed in claim 1, it is characterized in that the random polymeric amide B that obtains with unsaturated aliphatic dimeracid and short-chain diamine reaction is a basic raw material, basic raw material B and aliphatic long-chain diprotic acid A carry out mass polymerization, carry out partial cross-linkedly again with aliphatie diamine, make the hot-melting type polymeric amide.
3. in accordance with the method for claim 2, it is characterized in that building-up reactions carries out under negative pressure.
4. in accordance with the method for claim 2, it is characterized in that synthesis reaction temperature is 150-300 ℃.
5. according to claim 2 or 4 described methods, it is characterized in that synthesising reacting time is 4-10 hour.
6. in accordance with the method for claim 2, it is characterized in that building-up reactions carries out under acidic conditions.
7. in accordance with the method for claim 2, both it is characterized in that can different carbon numbers mixed dibasic acid do reaction raw materials and react, also the polymeric amide that the differential responses thing can be generated mixes the back and uses.
8. in accordance with the method for claim 2, it is characterized in that in the bulk polymerization of random polymeric amide B and aliphatic long-chain diprotic acid A, the molar ratio of random polymeric amide B and aliphatic long-chain diprotic acid A is 1: 0.4～1.
9. in accordance with the method for claim 8, it is characterized in that generating intermediate product C by B and A mass polymerization, intermediate product C carries out polymerization with aliphatie diamine D again, and the charging capacity of aliphatie diamine D is the 80%-100% of theoretical value in the reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94116955A CN1066478C (en) | 1994-10-19 | 1994-10-19 | Polyamide hot-melt adhesive and its prepn. method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94116955A CN1066478C (en) | 1994-10-19 | 1994-10-19 | Polyamide hot-melt adhesive and its prepn. method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1121101A true CN1121101A (en) | 1996-04-24 |
| CN1066478C CN1066478C (en) | 2001-05-30 |
Family
ID=5038178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94116955A Expired - Fee Related CN1066478C (en) | 1994-10-19 | 1994-10-19 | Polyamide hot-melt adhesive and its prepn. method |
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| Country | Link |
|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1080752C (en) * | 1997-10-28 | 2002-03-13 | 四川省大邑热缩制品厂 | Thermal state high strength hot melt adhesive with polyamide or polyester amide structure |
| CN1102169C (en) * | 1999-09-29 | 2003-02-26 | 郑州大学 | Petroleum fermented nylon 1212 not-fusible colloid and its preparing process |
| CN100365092C (en) * | 2003-09-15 | 2008-01-30 | 中国石油化工股份有限公司 | Thermosol of polyamide and preparation process thereof |
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5262346A (en) * | 1975-11-18 | 1977-05-23 | Matsushita Electric Ind Co Ltd | Hot melt adhesive |
| JPS52146446A (en) * | 1976-05-31 | 1977-12-06 | Denki Onkyo Co Ltd | Flameeretardant hottmelt adhesive |
-
1994
- 1994-10-19 CN CN94116955A patent/CN1066478C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1080752C (en) * | 1997-10-28 | 2002-03-13 | 四川省大邑热缩制品厂 | Thermal state high strength hot melt adhesive with polyamide or polyester amide structure |
| CN1102169C (en) * | 1999-09-29 | 2003-02-26 | 郑州大学 | Petroleum fermented nylon 1212 not-fusible colloid and its preparing process |
| CN100365092C (en) * | 2003-09-15 | 2008-01-30 | 中国石油化工股份有限公司 | Thermosol of polyamide and preparation process thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1066478C (en) | 2001-05-30 |
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