CN1156551C - Polyamide thermosol and its prepn - Google Patents
Polyamide thermosol and its prepn Download PDFInfo
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- CN1156551C CN1156551C CNB011060344A CN01106034A CN1156551C CN 1156551 C CN1156551 C CN 1156551C CN B011060344 A CNB011060344 A CN B011060344A CN 01106034 A CN01106034 A CN 01106034A CN 1156551 C CN1156551 C CN 1156551C
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- diprotic acid
- acid
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Abstract
The present invention provides a polyamide hot-melt adhesive and a preparing method thereof. Raw materials in the existing method are selected, and technology is optimized so that the tenacity and the flame resisting properties of a product are further improved to obtain a flame resisting hot-melt adhesive which has the advantages of narrow fusion ranges, a high softening point, excellent electrical properties and excellent tenacity.
Description
The present invention relates to a kind of polyamide hot and preparation method thereof, particularly polyamide hot of good stability and preparation method thereof.
Hot melt adhesive with high softening-point, narrow fusion range, excellent toughness, especially polyamide-based hot melt adhesive can be used for being adhesively fixed of electronic devices and components such as televisor deflector coil, air filter for automobile bonding, the bonding and multiple porous of metallic substance and non-porous material bonding.Usually as Hotmelt Adhesive and have than the polymeric amide of high softening-point and mainly carry out binary or terpolymer and get, be as Japanese Patent JP59-126483 polymeric amide repeating unit by aromatic diacid and aromatic series or long-chain fat family diamines:
Wherein: R is-(CH
2)
6-12-, Ar is a phenyl.Also adopted in the U.S. Pat 5089588 with the phenyl is 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, in these methods, generally use solvent polymeric, can bring problems such as product separation, solvent recuperation in these methods of industrial enforcement, simultaneously, also can cause certain environmental pollution.
Chinese patent CN1121101A has overcome the weak point of above-mentioned patent, the random polymeric amide that obtains with unsaturated aliphatic dimeracid and short-chain diamine reaction is a basic raw material, carry out bulk polymerization with long-chain fat family diprotic acid, aliphatie diamine, the softening temperature and the toughness of product have been improved, solve the environmental problem in producing, also can realize the flame retardancy of product.But, because the diprotic acid that it adopts is a long-chain fat family diprotic acid, and long-chain fat family base is bigger than the transport property of aromatic series or alicyclic group, long-chain fat family base migration recrystallization simultaneously, moves the ratio that forms hydrogen bond between the amide group that makes in the polymeric amide molecule and increases, thereby As time goes on, the lattice trend regularization of polyamide resin causes its toughness to reduce, and it is big that fragility becomes.So the toughness of products of CN1121101A is the toughness of products of patents such as relative JP59-126483 and US5089588 improvement is arranged, and As time goes on, it is big that the polymeric amide fragility that synthesizes becomes, snappiness reduces.
The objective of the invention is on the technical foundation of CN1121101A, provide a kind of toughness higher, stable better flame retardancy hot-melting type polyamide product and preparation method thereof.
The present invention is a basic raw material with polymeric amide A, carries out bulk reaction with diprotic acid B of long-chain fat family and alicyclic diprotic acid C and generates intermediate product D, and intermediate product D carries out crosslinking reaction with aliphatie diamine E again, obtains product of the present invention.
In aforesaid method, the feed ratio of reactant A, B+C, E is: 1: 2-4: 0.8-1.2 (mol ratio).The feed ratio of aliphatic dibasic acid B and alicyclic diprotic acid C is 1: 0.1-0.3 (mol ratio), preferably 1: 0.2-0.28.Diprotic acid B and C can add in the reactive system simultaneously, also can add respectively in the reactive system, and sequencing can not need limit, but for easy to operate, preferably add simultaneously.
Before intermediate product D and aliphatie diamine E carry out crosslinking reaction, preferably add chemical toughner F and carry out toughness reinforcing crosslinking reaction, the charging capacity of chemical toughner F is 30%～75% of a theoretical value, is preferably 40%～60%.Above-mentioned chemical toughner F is polyethers or the rubber-like material that has active group, rubber-like material such as carboxyl end of the liquid acrylonitrile-butadiene rubber or hydroxyl terminated butyl nitrile (HTBN) rubber etc., and polyether substance is as 220 polyethers, 330 polyethers, 403 polyethers or 505 polyethers etc.
The theoretical value calculation formula of chemistry toughner F is: W
E=M
EW
B/ NM
B, in the formula:
W
ETheoretical charging capacity M for toughner E
DMolecular weight for toughner E
W
BActual charging capacity M for feedstock fat family diprotic acid
BMolecular weight for feedstock fat family diprotic acid
N is an active group number in the toughner molecule.
The raw material polymeric amide that is fit to the inventive method is that softening temperature is 80-130 ℃, acid number＜6, and the polymeric amide of amine value＜6, acid is C
6-C
36Aliphatics saturated or unsaturated dibasic acid and alicyclic diprotic acid and dimeracid, amine is C
2-C
12Aliphatie diamine.Can mix with two or more diprotic acid and react, amine also can adopt the blended aliphatie diamine to react.Common alicyclic diprotic acid is 1, the 4-cyclohexyl dicarboxylic acid.
Generated time of the present invention is 0.5-10 hour, preferably 2-4 hour.In order to remove the water of generation, guarantee to react and carry out smoothly, building-up reactions is preferably in negative pressure carries out, and vacuum tightness is 500-760mmHg, is preferably 680-720mmHg.Raw material is participated in reaction with molten state, and its synthesis reaction temperature is preferably between 170-280 ℃.Building-up reactions of the present invention is carried out under acidic conditions, and the reaction times is no less than 0.5 hour, is preferably 2-4 hour.
Most of structural unit of product of the present invention is:
The small portion structural unit is:
Wherein: A is the low molecular polyamides base, R
4For-(CH
2)
2-12-, R
3For-(CH
2)
6-13, R
5Be alicyclic radical.The content of two kinds of structural units in product is decided by ingredient proportion and level of response, also has some other structural units in addition in the product, as
Contain ester group and ether structural unit (its concrete structure is by adding toughner decision) because the adding of chemical toughner F also may be introduced part, these structural units are decided by ingredient proportion at the content of product.
Owing to used the alicyclic diprotic acid of part to be raw material, make and introduce a small amount of alicyclic group in the product hot melt adhesive, reduced the migration probability, simultaneously because the sterically hindered effect of alicyclic group, hindered between the amide group in the polymeric amide molecule and form hydrogen bond, thereby the toughness that guarantees product can not change along with the time.The consumption of alicyclic diprotic acid will be controlled proper, and consumption is too many, and then product becomes fragile, and consumption is very few, and then the stability of toughness of products can not get improving.Chemical toughner F among the present invention is the rubber-like material that polyethers or end group have active group, ehter bond itself is flexible fabulous atomic radical, and the toughness of rubber-like material is very good, and they are introduced in the polymeric amide molecule, not only snappiness can be improved, its winter hardiness can also be improved.This chemistry toughner F added before adding diamines, its active hydroxyl and the carboxyl generation alkyd condensation reaction that does not have reaction, generate snappiness ester group preferably, the diamines that the back adds plays linking agent, in the polymeric amide that synthesizes like this owing to introduce a spot of flexible chain ester bond and ehter bond, thereby its toughness is further improved on the product basis of CN1121101A, again because the space structure of chemical toughner is non-straight chain, so produce space steric effect, further hinder the intermolecular formation hydrogen bond of polymeric amide, make the toughness of polymeric amide increase and kept.
Product snappiness of the present invention be improved significantly, softening temperature significantly improves, fusion range is narrow, the toughness good stability, the flame retardancy of product reaches UL-94 V-0 level, and does not contain deleterious aromatics, the product nontoxicity.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, cuts down the consumption of energy, and alleviates environmental pollution.
Product of the present invention can use separately, also two kinds of different material reaction products therefroms can be mixed and use.Also can be as required, further with the composite use of mineral filler, to satisfy different service requirementss, can be used for being adhesively fixed of electronic devices and components such as televisor deflector coil, air filter for automobile bonding, the bonding and multiple porous of metallic substance and non-porous material bonding is specially adapted to some toughness and anti-envrionment temperatures to adhesives and requires high, fusion range requires narrow, and electrical property and flame retardancy require harsh occasion.
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
With polymeric amide A (commodity are called 011 resin, 110 ℃ of softening temperatures, acid number＜6, amine value＜6) and C
10Diprotic acid B and 1,4-cyclohexyl dicarboxylic acid C mixes, add band and vacuumize in the reactor with condenser system, add the phosphoric acid (purity 85%) of 0.05% (W), under agitation be warmed up to 260 ℃, reacted 1 hour, vacuum tightness is 600mmHg, and reaction mass is cooled to 190 ℃, adds the phosphoric acid (purity is greater than 85%) of hexanediamine E and 0.05%, the molar ratio of A, B+C, E is 1: 2: 0.8, and wherein the mol ratio of B and C is 1: 0.1.React half an hour under this temperature, be warming up to 250 ℃ then and reacted 1 hour under the state of vacuumizing, vacuum tightness is 600mmHg, products obtained therefrom is brown transparent thick liquid, be the toughness solid, 154 ℃ of softening temperatures, viscosity (200 ℃) 510mPa.S after being cooled to room temperature.
Embodiment 2
Under the operational condition of embodiment 1, change B into C
13Diprotic acid, charging capacity change A, B+C into, the E mol ratio is 1: 4: 0.8, and wherein the mol ratio of B and C is 1: 0.2.
Embodiment 3
Under the operational condition of embodiment 1, change B into C
18The dimeracid of unsaturated fatty acids (is equivalent to C
36Diprotic acid) and C
6The mixture of diprotic acid (mixing mol ratio is 4: 6), charging capacity changes A, B+C into, the E mol ratio is 1: 3: 0.84, and wherein B and C's is 1: 0.3.
Embodiment 4
Under the operational condition of embodiment 2, change E into quadrol, the molar ratio of A and E is 1: 1.0.
Embodiment 5
Under the operational condition of embodiment 1, change E the mixture (ratio of mixture is 1: 3) of quadrol and hexanediamine into, the molar ratio of A and E is 1: 1.2.
Embodiment 6
The product that will obtain respectively under the condition of embodiment 1 and 5 mixed by 1: 4.
Embodiment 7
Product and AL (OH) with embodiment 4
3Mix with 3: 2 (W).
Embodiment 8
With low molecular polyamides A (commodity are called 011 resin, softening temperature 80-130 ℃, acid number＜6, amine value＜6) and C
10Diprotic acid B and 1,4-cyclohexyl dicarboxylic acid C mixes, adding band vacuumizes in the reactor with condenser system, drip the phosphoric acid (purity is 85%) of 0.05% (W), under agitation be warmed up to 260 ℃, reacted 1 hour, vacuum tightness is 600mmHg, reaction mass is cooled to 190 ℃, add 330 polyethers F of 60% theoretical consumption and the phosphoric acid of hexanediamine E and 0.05% (purity is 85%), react half an hour under this temperature, be warming up to 250 ℃ then and reacted 1 hour under the state of vacuumizing, vacuum tightness is 600mmHg.The mol ratio of above-mentioned raw materials A, B+C, E is 1: 2: 0.8, and wherein the mol ratio of B and C is 1: 0.1.Products obtained therefrom is the red-brown thick liquid, is cooled to be toughness solid, 153.5 ℃ of softening temperatures, viscosity (200 ℃) 618mPa.S after the room temperature.
Embodiment 9
Under the operational condition of embodiment 1, change B into C
13Diprotic acid, toughner F changes 220 polyethers into, and the charging capacity of F changes 30% of theoretical value into.
Embodiment 10
Under the operational condition of embodiment 1, change B into C
18The dimeracid of unsaturated fatty acids (is equivalent to C
36Diprotic acid) and C
10The mixture of diprotic acid (mixing mol ratio is 3: 1), F changes 505 polyethers into, and the charging capacity of F changes 75% of theoretical value into, and the molar ratio of B and C changes 1: 0.2 into.
Embodiment 11
Under the operational condition of embodiment 1, E changes quadrol into, and the mol ratio of raw material A, B+C, E is 1: 3: 1, and wherein the mol ratio of B and C is 1: 0.28.
Embodiment 12
Under the operational condition of embodiment 1, E changes decamethylene diamine into, and the first step reaction is after 1 hour, and the second step temperature of reaction is reduced to 130 ℃.The mol ratio of raw material A, B+C, E is 1: 4: 1.2, and wherein the mol ratio of B and C is 1: 0.3.
Embodiment 13
The product that will obtain respectively under the condition of embodiment 1 and 5 mixed by 1: 4.
The foregoing description products obtained therefrom is listed in table 1.
Each embodiment product property of table 1
| Embodiment | Softening temperature (℃) | Melt viscosity (200 ℃ of mpa.S) | Flame retardancy (UL-94) | Low-temperature performance (5 ℃) | Shearing resistance (AL-AL, M Pa) | Low temperature properties after 6 months (5 ℃) |
| 1 | ?154 | ?510 | ?V-0 | Do not fracture | ?5.7 | Do not fracture |
| 2 | ?156 | ?600 | ?V-0 | Do not fracture | ?6.0 | Do not fracture |
| 3 | ?157.5 | ?620 | ?V-0 | Do not fracture | ?6.1 | Do not fracture |
| 4 | ?155 | ?732 | ?V-0 | Do not fracture | ?7.0 | Do not fracture |
| 5 | ?158 | ?960 | ?V-0 | Do not fracture | ?7.8 | Do not fracture |
| 6 | ?156 | ?813 | ?V-0 | Do not fracture | ?6.4 | Do not fracture |
| 7 | ?155.5 | ?2693 | ?V-0 | Do not fracture | ?8.6 | Do not fracture |
| 8 | ?153.5 | ?618 | ?V-0 | Do not fracture | ?6.9 | Do not fracture |
| 9 | ?152 | ?492 | ?V-0 | Do not fracture | ?5.7 | Do not fracture |
| 10 | ?158 | ?1280 | ?V-0 | Do not fracture | ?9.1 | Do not fracture |
| 11 | ?157.5 | ?937 | ?V-0 | Do not fracture | ?7.3 | Do not fracture |
| 12 | ?161 | ?2150 | ?V-0 | Do not fracture | ?8.5 | Do not fracture |
| 13 | ?159 | ?1200 | ?V-0 | Do not fracture | ?7.0 | Do not fracture |
The experimental technique explanation:
Softening temperature-ASTM 28-58T
Viscosity-ASTM D2069-77
Flame retardancy-UL-94
Low-temperature performance (5 ℃)-laboratory method: the glue sample is prepared the adhesive tape of growth 5cm, wide 1cm, thick 0.2cm, and the glue sample is put under 5 ℃ the environment, and constant temperature 4 hours with record book in accordion form glue sample, breaks into poor performance at low temperatures, and it is passable not break into low-temperature performance.
Shearing resistance-ASTM D1002-72
Claims (11)
1, a kind of polyamide hot, with polymeric amide A is basic raw material, carry out bulk reaction with diprotic acid and generate intermediate product D, intermediate product D carries out crosslinking reaction with aliphatie diamine E again, get the hot melt adhesive product, it is characterized in that wherein diprotic acid is the mixture of diprotic acid B of long-chain fat family and alicyclic diprotic acid C, wherein the diprotic acid B of long-chain fat family is C
6-C
36Long-chain fat family diprotic acid, alicyclic diprotic acid C is 1,4-cyclohexyl dicarboxylic acid, aliphatie diamine E are C
2-C
10Aliphatie diamine.
According to the described polyamide hot of claim 1, it is characterized in that 2, the molar ratio of reactant A, B+C, E is 1: 2-4: 0.8-1.2, wherein the molar ratio of aliphatic dibasic acid B and alicyclic diprotic acid C is 1: 0.-0.3.
3, according to the described polyamide hot of claim 2, the molar ratio that it is characterized in that described aliphatic dibasic acid B and alicyclic diprotic acid C is 1: 0.2-0.28.
4, according to the described polyamide hot of claim 1, the softening temperature that it is characterized in that described raw material polymeric amide A is 80-130 ℃, acid number＜6, amine value＜6.
5, according to the described polyamide hot of claim 1, it is characterized in that reaction conditions is: vacuum tightness is 500-760mmHg, and raw material is participated in reaction with molten state, and building-up reactions is carried out under acidic conditions, and the reaction times is 0.5-10 hour.
6, according to claim 1 or 7 described polyamide hots, it is characterized in that reaction conditions is: vacuum tightness is 680-720mmHg, and temperature of reaction is 170-280 ℃, and the reaction times is 2-4 hour.
7,, it is characterized in that before intermediate product D and aliphatie diamine E carry out crosslinking reaction, adding chemical toughner F and carry out toughness reinforcing crosslinking reaction according to the described polyamide hot of claim 1.
8, according to the described polyamide hot of claim 7, the charging capacity that it is characterized in that chemical toughner F is 30%～75% of a theoretical value.
9,, it is characterized in that described chemical toughner F is polyethers or the rubber-like material that has active group according to the described polyamide hot of claim 7.
10, according to the described polyamide hot of claim 9, it is characterized in that described rubber-like material is carboxyl end of the liquid acrylonitrile-butadiene rubber or hydroxyl terminated butyl nitrile (HTBN) rubber, described polyether substance is 220 polyethers, 330 polyethers, 403 polyethers or 505 polyethers.
13, according to the described polyamide hot of claim 9, the charging capacity that it is characterized in that described toughner F is 40%～60% of a theoretical value.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011060344A CN1156551C (en) | 2001-01-05 | 2001-01-05 | Polyamide thermosol and its prepn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011060344A CN1156551C (en) | 2001-01-05 | 2001-01-05 | Polyamide thermosol and its prepn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1362460A CN1362460A (en) | 2002-08-07 |
| CN1156551C true CN1156551C (en) | 2004-07-07 |
Family
ID=4655092
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011060344A Expired - Lifetime CN1156551C (en) | 2001-01-05 | 2001-01-05 | Polyamide thermosol and its prepn |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1156551C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210163B (en) * | 2006-12-27 | 2012-01-11 | 上海理日化工新材料有限公司 | Monocomponent polyurethane adhesive and metal film coated plate bonded by the same |
-
2001
- 2001-01-05 CN CNB011060344A patent/CN1156551C/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| CN1362460A (en) | 2002-08-07 |
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