CN1162496C - Modified polyamide thermosol - Google Patents
Modified polyamide thermosol Download PDFInfo
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- CN1162496C CN1162496C CNB01114176XA CN01114176A CN1162496C CN 1162496 C CN1162496 C CN 1162496C CN B01114176X A CNB01114176X A CN B01114176XA CN 01114176 A CN01114176 A CN 01114176A CN 1162496 C CN1162496 C CN 1162496C
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- diprotic acid
- alicyclic
- hot
- long
- 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 modified so that the tenacity and the fire-retarding properties of a product are further improved to obtain a fire-retarding hot-melt adhesive which has the advantages of narrow fusion ranges, high softening point, excellent electrical properties and tenacity.
Description
The present invention relates to a kind of modified polyamide thermosol 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.
Polyamide hot of the present invention is a basic raw material with polymeric amide A, carries out bulk reaction with diprotic acid B and generates intermediate product C, and intermediate product C and alicyclic diamine E, aliphatie diamine F carry out toughness reinforcing crosslinking reaction, make the hot-melting type polymeric amide.
Above-mentioned intermediate product C with the diamines crosslinking reaction before, can be earlier and chemical toughner D reaction.Above-mentioned diprotic acid B is the diprotic acid G of long-chain fat family or the diprotic acid G of long-chain fat family and two kinds of diprotic acid of alicyclic diprotic acid H.Reaction of the present invention also can take toughner D and two technical essentials of two kinds of diprotic acid to use simultaneously.
In the methods of the invention, the molar ratio of reactant A, B, E+F is: A: B: E+F=1: 2～4: 0.8～1.2 (mol ratio) is preferably A: B: E+F=1: 2～4: 0.8～1.0.The charging capacity of chemistry toughner D is 10%～75% of a theoretical value, and the calculation formula of its theoretical value 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.
The raw material polymeric amide that is fit to the inventive method is low molecular polyamides A, and its softening temperature is 80-130 ℃, acid number＜6, amine value＜6; Diprotic acid B is C
6-C
36Aliphatics saturated or unsaturated dibasic acid or dimeracid, amine is C
2-C
12Aliphatie diamine F and alicyclic diamine E.Can react separately with a kind of diprotic acid, also can mix with two or more diprotic acid and react, mix use after also can adopting two or more different diprotic acid and the raw material polymeric amide reacting respectively, diamines also can mix use.The feed ratio of alicyclic diamine E and aliphatie diamine F is 0.1～0.3: 1 (mol ratio), preferably 0.15～0.25: 1.Common alicyclic diamine E is a 4 etc.Diprotic acid B can be aliphatic dibasic acid G, also can adopt aliphatic dibasic acid G and two kinds of diprotic acid of alicyclic diprotic acid H.The mol ratio of diprotic acid G of long-chain fat family and alicyclic diprotic acid H is 1: 0.1-0.3 is preferably 1: 0.2-0.28, alicyclic diprotic acid H commonly used is 1, the 4-cyclohexyl dicarboxylic acid.Two types diamines or diprotic acid can add reactive system simultaneously, also can add reactive system respectively, and sequencing need not limit, but are easy to operate preferably adding simultaneously.
In the method for the invention, chemistry toughner D is polyethers or the rubber-like (as carboxyl end of the liquid acrylonitrile-butadiene rubber, hydroxyl terminated butyl nitrile (HTBN) rubber, 220 polyethers, 330 polyethers, 403 polyethers, 505 polyethers etc.) that has active group (as hydroxyl, carboxyl), charging capacity preferably theoretical value 40%～60%.
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 580～730mmHg.Raw material is participated in reaction with molten state, and its synthesis reaction temperature is preferably between 130～250 ℃.Building-up reactions is carried out under acidic conditions, and the reaction times is 0.5～10 hour, is preferably 2～4 hours.
Most of structural unit of product of the present invention is:
Have the sub-fraction structural unit to be:
Wherein: A is the low molecular polyamides base, R
4For-(CH
2)
2-12-, R
3For-(CH
2)
6-13, R
5Be alicyclic radical.Also has to contain ester group and ether (its concrete structure is by adding toughner decision) in the sub-fraction structural unit, and some other structural units the type of these structural units and decide by feed intake type and ratio at the content of product.
Introduce a small amount of alicyclic group in the product of the present invention, 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 diamine E will be controlled proper, and consumption is many slightly, and then product becomes fragile, and consumption is very few, and then the stability of toughness of products can not get improving.When adding alicyclic diamine, can add chemical toughner D and alicyclic diprotic acid.Chemistry toughner can be 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 D 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.The effect of alicyclic diprotic acid and the effect of alicyclic diamine are similar, two kinds of cooperations can further improve product stability.
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 aromatics.
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 being adhesively fixed of electronic devices and components such as televisor deflector coil, air filter for automobile bonding, bonding and the multiple porous of metallic substance and non-porous material bonding, be specially adapted to some toughness and anti-envrionment temperatures to adhesives and require height, fusion range requires 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, cuts down the consumption of energy, and alleviates environmental pollution.
Method of the present invention is simple, and is free from environmental pollution, can be used for synthetic various types of polymeric amide, particularly hot-melting type polymeric amide.
Specify product of the present invention and method by the following examples.
Embodiment 1
With low molecular polyamides (A) (commodity are called 011 resin, 110 ℃ of softening temperatures) and C
10Diprotic acid (B) mixed in 1: 2 in molar ratio, adding band vacuumizes in the reactor with condenser system, the vacuum degree control value is 650mmHg, drip the phosphoric acid (purity is 85%) of 0.05% (W), under agitation be warmed up to 260 ℃, reacted 1 hour, reaction mass is cooled to 190 ℃, add 330 polyethers (D) of 60% theoretical consumption and the hexanediamine (F) of 0.73mol, 0.073mol 4,4 '-diamino-dicyclohexyl methane (E) (is that the entire reaction feed ratio is A: B: E+F=1: 2: 0.8,1) and 0.05% phosphoric acid (purity is 85%) E: F=0.1 wherein:, under this temperature, react half an hour, be warming up to 250 ℃ of reactions 1 hour under the state of vacuumizing then, products obtained therefrom is the red-brown thick liquid, be the toughness solid, 147 ℃ of softening temperatures, viscosity (200 ℃) 738mPa.S after being cooled to room temperature.
Embodiment 2
Under the operational condition of embodiment 1, change B into C
13Diprotic acid, toughner D changes 220 polyethers into, and the charging capacity of 220 polyethers changes 30% of theoretical value into.
Embodiment 3
Under the operational condition of embodiment 1, change B into C
18The dimeracid of unsaturated fatty acids and C
10The mixture of diprotic acid (ratio of mixture is 3: 1), D changes 505 polyethers into, and the charging capacity of 505 polyethers changes 75% of theoretical value into, and the molar ratio of E and F changes 0.2: 1 into.
Embodiment 4
Under the operational condition of embodiment 1, change the molar ratio of A, B, E+F into A: B: E+F=1: 3: 1, F changed quadrol into.
Embodiment 5
Under the operational condition of embodiment 1, change the molar ratio of A, B, E+F into A: B: E+F=1: 4: 1.0, F changed decamethylene diamine into, and the molar ratio of E and F changes 0.22: 1 into, reacted after 1 hour, and the second step temperature of reaction is reduced to 130 ℃.
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
Under the operational condition of embodiment 5, feed ratio changes A into: B: E+F=1: 4: 1.2, F changed decamethylene diamine into, and the molar ratio of E and F changes 0.3: 1 into, did not use toughner.
Embodiment 9
Under the operational condition of embodiment 3, E wherein and F molar ratio change 0.1: 1 into, and diprotic acid B wherein changes C into
10Diprotic acid G and 1,4-cyclohexyl dicarboxylic acid H mol ratio is 1: 0.1 a mixture, and toughner D wherein is a hydroxyl terminated butyl nitrile (HTBN) rubber, and dosage is 15% of a theoretical value.
Embodiment 10
Under the operational condition of embodiment 3, do not use toughner, E wherein and F molar ratio change 0.1: 1 into, and diprotic acid B wherein changes C into
13Diprotic acid and 1,4-cyclohexyl dicarboxylic acid mol ratio are 1: 0.3 mixture.
Comparative example is an alternative with the embodiment 1 of CN1121101A.
The foregoing description and comparative example products obtained therefrom are listed in table 1.
Table 1
| Embodiment | Softening temperature, ℃ | Melt viscosity, 200 ℃ of mPa.S | Flame retardancy, UL-94 | Low-temperature performance, 5 ℃ | Shearing resistance, AL-AL, MPa | Low temperature properties after 6 months, 5 ℃ |
| 1 | ?147 | ?738 | ?V-0 | Do not fracture | 5.9 | Do not fracture |
| 2 | ?145.5 | ?518 | ?V-0 | Do not fracture | 5.7 | Do not fracture |
| 3 | ?151 | ?962 | ?V-0 | Do not fracture | 7.1 | Do not fracture |
| 4 | ?154.5 | ?895 | ?V-0 | Do not fracture | 6.2 | Do not fracture |
| 5 | ?158 | ?1140 | ?V-0 | Do not fracture | 6.6 | Do not fracture |
| 6 | ?156.5 | ?1071 | ?V-0 | Do not fracture | 6.1 | Do not fracture |
| 7 | ?157 | ?3000 | ?V-0 | Do not fracture | 7.4 | Do not fracture |
| 8 | ?160 | ?1300 | ?V-0 | Do not fracture | 5.6 | Do not fracture |
| 9 | ?150.5 | ?974 | ?V-0 | Do not fracture | 6.4 | Do not fracture |
| 10 | ?148 | ?690 | ?V-0 | Do not fracture | 6.8 | Do not fracture |
| Comparative example | ?154 | ?640 | ?V-0 | Do not fracture | 7.1 | 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 (10)
1, a kind of polyamide hot is a basic raw material with polymeric amide A, carries out bulk reaction with diprotic acid B and generates intermediate product C, and intermediate product C and alicyclic diamine E, aliphatie diamine F carry out toughness reinforcing crosslinking reaction, make the hot-melting type polymeric amide.
2, according to the described polyamide hot of claim 1, it is characterized in that described intermediate product C with the diamines crosslinking reaction before, earlier with chemical toughner D reaction.
3,, it is characterized in that described diprotic acid B is the diprotic acid G of long-chain fat family or diprotic acid G of long-chain fat family and alicyclic diprotic acid H according to the described polyamide hot of claim 1.
4,, it is characterized in that described diprotic acid B is the diprotic acid G of long-chain fat family or diprotic acid G of long-chain fat family and alicyclic diprotic acid H according to the described polyamide hot of claim 2.
5,, it is characterized in that described material molar ratio is A: B: E+F=1 according to the described polyamide hot of claim 1: 2～4: 0.8～1.2, wherein the mol ratio of E and F is 0.1-0.3: 1.
6, according to claim 2 or 4 described polyamide hots, the add-on that it is characterized in that described toughner D is 10%～75% of a theoretical value.
7, according to claim 3 or 4 described polyamide hot melt adhesives, the mol ratio that it is characterized in that described long-chain fat family's diprotic acid and alicyclic diprotic acid is 1: 0.1-0.3.
8,, it is characterized in that acid number＜6, amine value＜6, softening temperature 80-130 ℃ of described raw material polymeric amide according to claim 1,2,3 or 4 described polyamide hots.
9, according to the described polyamide hot of claim 1, it is characterized in that described alicyclic diamine E is a 4, aliphatie diamine F is C
2-C
12Aliphatie diamine in one or more.
10, according to claim 2 or 4 described polyamide hots, it is characterized in that described toughner D is polyethers or the rubber-like material that has active group hydroxyl or carboxyl, its charging capacity is 40%～60% of a theoretical charging capacity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB01114176XA CN1162496C (en) | 2001-07-02 | 2001-07-02 | Modified polyamide thermosol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB01114176XA CN1162496C (en) | 2001-07-02 | 2001-07-02 | Modified polyamide thermosol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1393501A CN1393501A (en) | 2003-01-29 |
| CN1162496C true CN1162496C (en) | 2004-08-18 |
Family
ID=4660847
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB01114176XA Expired - Lifetime CN1162496C (en) | 2001-07-02 | 2001-07-02 | Modified polyamide thermosol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1162496C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11570876B2 (en) | 2016-11-04 | 2023-01-31 | Luminaid Lab, Llc | Solar lamps with radial elements |
| US11592147B2 (en) | 2012-05-01 | 2023-02-28 | Luminaid Lab Llc | Expandable solar-powered light |
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
- 2001-07-02 CN CNB01114176XA patent/CN1162496C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11592147B2 (en) | 2012-05-01 | 2023-02-28 | Luminaid Lab Llc | Expandable solar-powered light |
| US11570876B2 (en) | 2016-11-04 | 2023-01-31 | Luminaid Lab, Llc | Solar lamps with radial elements |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1393501A (en) | 2003-01-29 |
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