CN1264894C - Low molecular polyamide modified hot melt adhesive and method for preparation - Google Patents
Low molecular polyamide modified hot melt adhesive and method for preparation Download PDFInfo
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- CN1264894C CN1264894C CN 200410066137 CN200410066137A CN1264894C CN 1264894 C CN1264894 C CN 1264894C CN 200410066137 CN200410066137 CN 200410066137 CN 200410066137 A CN200410066137 A CN 200410066137A CN 1264894 C CN1264894 C CN 1264894C
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- versamid
- melt adhesive
- reaction
- grafting
- modified hot
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Abstract
The present invention relates to versamid modified hot-melt adhesive and a preparation method thereof. In the preparation method, the versamid is obtained by way of modification through the steps of stem grafting and cross linking. Versamid and grafting agents are proportionally added into a reaction kettle with vacuum and a condensing system, temperature rises during agitation, prepolymers are obtained after grafting reaction is carried out, cross-linking agents are added proportionally to carry out temperature reaction for a plurality of hours after the processes of vacuum pumping and temperature drop, and versamid modified hot-melt adhesive is obtained after cross-linking reaction is carried out. The present invention adopts a two-step method for bulk polymerization, no pollution is caused in production, and both solvent recovery and product purification are avoided, so that the manufacturing process is simplified. Home-made 010 resin or 011 resin is adopted as the raw material, which achieves low cost and rich resources. Both the softening point and the viscosity can be adjusted by changing technological conditions. Dihydric alcohol or polyatomic alcohol is adopted for replacing diamine in the formulation, which reduces the chance of forming hydrogen bonds in macromolecules and enhances the flexibility of products.
Description
Technical field
The present invention relates to have the polyesteramide of hotmelt character, refer in particular to a kind of low molecular polyamide modified hot melt adhesive and make each method.
Background technology
Usually have than high softening-point and polymeric amide hotmelt, how carry out binary or multi-component copolymer and get by aromatic diacid and aromatic series or aliphatie diamine with better flowability.All adopting with the phenyl as Japanese Patent JP59-125483 and U.S. Pat 5089588 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, 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.
Chinese patent 94116955.3 has overcome the deficiency of above-mentioned patent, introduced the synthetic of a kind of polyamide hot, its characteristics are that with random polymeric amide be basic raw material, with the diprotic acid polymerization of long-chain fat family, again with the partial cross-linked hot-melting type polymeric amide that makes of aliphatie diamine.This method adopts mass polymerization, ties the problem of environmental pollution of having determined in producing, and has improved the snappiness of product.But because this method adopts long-chain fat family diacid, and long-chain fat family diacid is deposited the easy migration recrystallization that takes place in the process at product, and the oriented crystalline of even number long-chain fat family diacid tendency is more serious, thereby causes the product snappiness to reduce.In addition, producing a large amount of hydrogen bonds between the macromolecular amido linkage also is the factor that the product snappiness is reduced, as shown in the formula:
R
R C＝O
R C＝O - - - - - H-N-R’
C＝O - - - H-N-R’
H-N-R’
The polyamide hot that other Chinese patent 01106037.9 is introduced, with polymeric amide A is basic raw material, generate C with binary aliphatic B acid polymerization, carry out crosslinking reaction with aliphatie diamine E again and make the hot-melting type polymeric amide, its characteristics are: added chemical toughner D and carry out toughness reinforcing reaction before C and E reaction.Its toughner is the polyethers or the rubber-like of band active group.This way not only makes process complications, and increases cost.
Summary of the invention
At defective that exists in the prior art and deficiency, the problem to be solved in the present invention is regulated the sharp viscosity of softening temperature for improving the product snappiness, improves high temperature oxidation resisting, reduces material cost, simplifies production technique and solves environmental pollution.
The objective of the invention is provides a kind of good toughness on the basis of Chinese patent 94116955.3 and Chinese patent 01106037.9, the softening temperature height is anti-oxidant, the flame retardant type Low-molecular-weight Polyamide Modified Hot-melt Adhesive And Its Preparation Method.
Low molecular polyamide modified hot melt adhesive of the present invention is characterized in that having following repeat unit structure:
Wherein: R
1Be dimeracid, R
2For-(CH
2)-
2-12, R
3For-(CH
2)-
6-13, R4 be molecular weight be 60-2000-(CH
2)-or-(C
2H
40)
nCH
2-.
The method for preparing low molecular polyamide modified hot melt adhesive of the present invention is through grafting, crosslinked two step modifications and get with a kind of Versamid, its concrete steps are: earlier Versamid and grafting agent are added in the reactor of band vacuum and condenser system in proportion, stirring heats up down carries out graft reaction, must give aggressiveness, vacuumize, cooling adds linking agent temperature reaction a few hours more in proportion, carry out crosslinking reaction, sub-polyamide modified hot melt adhesive makes low score.Being fit to Versamid of the present invention is homemade 010 resin or 011 resin; Used grafting agent is aliphatics monounsaturated dicarboxylic acid or unsaturated dibasic acid, and its carbon atom number is 6～13; Used linking agent is that used linking agent is single alcohol or blended alcohol, and its molecular weight is 60～2000; Wherein can be dibasic alcohol or polyvalent alcohol or polymeric dihydric alcohol; Its raw material ratio is: Versamid: grafting agent: linking agent=1: 0.4～2.2: 0.2～2.0 (mol), and synthesis condition is: vacuum tightness 0.05～0.1MPa; 150～300 ℃ of temperature of reaction; Reaction times 1～11h.
The first step:
O O H H
H H H H
Second step:
O O H H
O＝C H H
R
1
O＝C-OH
The 3rd step: carry out suitable adjustment according to requirements of different users, obtain adapting to the product that different field is used.
Because the condenses of 010 resin system dimerization oleic acid and aliphatie diamine, reactive hydrogen in the molecule on the amide group N atom can be at a certain temperature, continue to make branchign of molecule by catalyst with the grafting agent reaction, generation has the aggressiveness that gives of reactive behavior, this gives aggressiveness again can be further and the linking agent condensation, and molecular weight is increased and buildization, and toughness is greatly enhanced, so just can reach the raising softening temperature, improve the effect of viscosity.
Detect the present invention through method for preparing and material, results of property is as follows:
| Project | Scope |
| Viscosity mPaS/190 ℃ | 1000～10000 |
| Softening temperature ℃ | 100～170 |
| Volume resistance Ω cm | ≥1×10 12 |
| Voltage breakdown KV/mm | ≥8.0 |
| Shearing resistance kg/cm 2Fe-Fe | ≥3.0 |
| Density | 1.28±0.05 |
| Flame retardancy UL-94 | V-O |
| Toughness (20 ℃, 5 ℃, 9 prints) | Not crooked fractureing |
The present invention adopts the two-step approach mass polymerization, and is pollution-free in the production, avoided solvent recuperation and product to purify, and technology is simple.Raw material adopts homemade 010 resin or 011 resin cost is low, the source abundant.Can regulate softening temperature, viscosity by changing processing condition.Replace diamine can reduce the chance that forms hydrogen bond in the macromole with dibasic alcohol or polyvalent alcohol in the prescription, improve the product snappiness.
Embodiment
Embodiment 1:
With Versamid, commodity are called 010 resin, and its softening temperature is 90～130 ℃, with C
6Diprotic acid, by 1: 0.6 mixed, add in the reactor of band vacuum and condenser system, stir and be warming up to 250 ℃ down and reacted one hour, vacuumized vacuum tightness 〉=0.08MPa then one hour.Be cooled to 160 ℃ after stopping to find time, and add the ethylene glycol of 0.8 times of 010 resin, be warming up to 250 ℃ of reactions 4 hours gradually.Products obtained therefrom is the brown viscous fluid, and the cooling back is the toughness solid, and softening temperature is 150 ℃, viscosity (190 ℃) 1600mpa.S;
The method for preparing low molecular polyamide modified hot melt adhesive of the present invention be with a kind of Versamid through crosslinked, two step modifications of grafting and get, used linking agent is dibasic alcohol or polyvalent alcohol, its molecular weight is 60～2000; Wherein can also can use blended alcohol with single alcohol; Used grafting agent is aliphatics monounsaturated dicarboxylic acid or unsaturated dibasic acid, and its carbon atom number is 6～13; Being fit to Versamid of the present invention is homemade 010 resin or 011 resin.Its raw material ratio is: Versamid: grafting agent: linking agent=1: 0.6: 0.8 (mol), and synthesis condition is: vacuum tightness 0.05～0.1MPa; 150～300 ℃ of temperature; Reaction times 1～11h.
Embodiment 2:
Under the operational condition of embodiment 1, with 010 resin and C
6Diprotic acid by 1: 1.8 mixed, wherein Versamid: grafting agent: linking agent=1: 1.8: 0.8 (mol);
Embodiment 3:
Under the operational condition of embodiment 1, with C
6Diprotic acid C
13Diprotic acid replaces, wherein Versamid: grafting agent: linking agent=1: 0.6: 0.8 (mol);
Embodiment 4:
Under the operational condition of embodiment 1, ethylene glycol is replaced with butyleneglycol, wherein Versamid: grafting agent: linking agent=1: 0.6: 0.8 (mol);
Embodiment 5:
Under the operational condition of embodiment 1, ethylene glycol is replaced with Macrogol 2000, wherein Versamid: grafting agent: linking agent=1: 0.6: 0.8 (mol);
Embodiment 6:
Under the operational condition of embodiment 1,010 resin and ethylene glycol are pressed 1: 1.6 mixed, wherein Versamid: grafting agent: linking agent=1: 0.6: 1.6 (mol);
Embodiment 7:
Under the operational condition of embodiment 1, ethylene glycol and mixed with propylene glycol is reinforced, and its blending ratio is 1.5: 1, wherein Versamid: grafting agent: linking agent=1: 0.6: 0.8 (mol);
Embodiment 8:
Under the operational condition of embodiment 1, add 30%Al (OH) 3; Then can adjust according to different needs, as: using aspect the televisor.
The performance of the foregoing description products obtained therefrom is listed in the table below:
| Embodiment | Softening temperature ℃ | Viscosity (190 ℃) mPa.S | Flame retardancy (UL-94) | Low-temperature flexibility (5 ℃, doubling 200 times) | Shearing resistance MPa |
| 1 | 150 | 1600 | The V-0 level | Not crooked fractureing | 6.8 |
| 2 | 148 | 1800 | The V-0 level | Not crooked fractureing | 7.0 |
| 3 | 153 | 2000 | The V-0 level | Not crooked fractureing | 7.5 |
| 4 | 160 | 3000 | The V-0 level | Not crooked fractureing | 7.2 |
| 5 | 130 | 6000 | The V-0 level | Not crooked fractureing | 7.5 |
| 6 | 145 | 1500 | The V-0 level | Not crooked fractureing | 6.5 |
| 7 | 150 | 2300 | The V-0 level | Not crooked fractureing | 8.2 |
| 8 | 155 | 3100 | The V-0 level | Not crooked fractureing | 9.4 |
Claims (3)
1. low molecular polyamide modified hot melt adhesive is characterized in that having following repeat unit structure:
Wherein: R
1Be dimeracid, R
2For-(CH
2)-
2 12, R
3For-(CH
2)-
6 13, R
4For molecular weight be 60-2000-(CH
2)-or-(C
2H
4O)
nCH
2-.
2. the preparation method of low molecular polyamide modified hot melt adhesive, it is characterized in that a kind of Versamid through grafting, crosslinked two step modifications and get, its concrete steps are: earlier Versamid and grafting agent are added in the reactor of band vacuum and condenser system in proportion, stirring heats up down carries out graft reaction, must give aggressiveness, vacuumizes, cooling, add linking agent temperature reaction a few hours more in proportion, carry out crosslinking reaction, sub-polyamide modified hot melt adhesive makes low score; Wherein being fit to Versamid of the present invention is homemade 010 resin or 011 resin; Used grafting agent is aliphatics monounsaturated dicarboxylic acid or unsaturated dibasic acid, and its carbon atom number is 6～13; Used linking agent is single alcohol or blended alcohol, and its molecular weight is 60～2000; Its raw material ratio is: Versamid: grafting agent: linking agent=1: 0.4～2.2: 0.2～2.0 (mol); Synthesis condition is: vacuum tightness 0.05～0.1MPa; 150～300 ℃ of temperature of reaction; Reaction times 1～11h.
3. the preparation method of low molecular polyamide modified hot melt adhesive according to claim 2 is characterized in that used linking agent is dibasic alcohol or polyvalent alcohol or polymeric dihydric alcohol.
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|---|---|---|---|
| CN 200410066137 CN1264894C (en) | 2004-12-09 | 2004-12-09 | Low molecular polyamide modified hot melt adhesive and method for preparation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410066137 CN1264894C (en) | 2004-12-09 | 2004-12-09 | Low molecular polyamide modified hot melt adhesive and method for preparation |
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|---|---|
| CN1635014A CN1635014A (en) | 2005-07-06 |
| CN1264894C true CN1264894C (en) | 2006-07-19 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8831406B2 (en) | 2002-11-20 | 2014-09-09 | Lg Electronics Inc. | Recording medium having data structure for managing reproduction of at least video data recorded thereon and recording and reproducing methods and apparatuses |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012777B (en) * | 2011-09-20 | 2016-01-06 | 上海杰事杰新材料(集团)股份有限公司 | A kind of High-temperature-ressemi-aromatic semi-aromatic polyamide, preparation method and application thereof |
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2004
- 2004-12-09 CN CN 200410066137 patent/CN1264894C/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8831406B2 (en) | 2002-11-20 | 2014-09-09 | Lg Electronics Inc. | Recording medium having data structure for managing reproduction of at least video data recorded thereon and recording and reproducing methods and apparatuses |
| US8886021B2 (en) | 2002-11-20 | 2014-11-11 | Lg Electronics Inc. | Recording medium having data structure for managing reproduction of at least video data recorded thereon and recording and reproducing methods and apparatuses |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1635014A (en) | 2005-07-06 |
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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 fulfillment period: 2007.11.30 to 2013.11.30 contract change Contract record no.: 2009320000180 Denomination of invention: Low molecular polyamide modified hot melt adhesive and method for preparation Granted publication date: 20060719 License type: Exclusive license Record date: 2009.3.2 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.11.30 TO 2013.11.30; CHANGE OF CONTRACT Name of requester: CHANGZHOU CITY BAOLI ADHESIVE CO., LTD. Effective date: 20090302 |
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Effective date of registration: 20141205 Address after: Daitou town of Liyang City Ferry Street 213311 Jiangsu city of Changzhou province 8-2 No. 7 Patentee after: Liyang Chang Technology Transfer Center Co., Ltd. Address before: 213016 Baiyun Road, Jiangsu, Changzhou Patentee before: Jiangsu Polytechnic University |