CN101503610B - Enclosed type self-crosslinking single component polyurethane binder and preparation thereof - Google Patents
Enclosed type self-crosslinking single component polyurethane binder and preparation thereof Download PDFInfo
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- CN101503610B CN101503610B CN 200810033516 CN200810033516A CN101503610B CN 101503610 B CN101503610 B CN 101503610B CN 200810033516 CN200810033516 CN 200810033516 CN 200810033516 A CN200810033516 A CN 200810033516A CN 101503610 B CN101503610 B CN 101503610B
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- encapsulant
- isocyanic ester
- polyvalent alcohol
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Abstract
The invention relates to a blocked self-crosslinking single-component polyurethane adhesive and a preparation method thereof. Raw materials of the adhesive comprise multifunctional isocyanate, a blocking agent and polylol, and the using amount of the raw materials meets the following formula: [1-NB/(cNC)](a-1-NB/NA) < [1/(c-1)], wherein NB represents the mole number of the blocking agent, c represents the functionality of the polylol, NC represents the mole number of the polylol, a represents the functionality of the multifunctional isocyanate, NA represents the mole number of the multifunctional isocyanate, and the a and the c are all more than or equal to 2. Compared with the prior art, the method adopts a little amount of blocking agent to perform partial blocking in advance on the multifunctional isocyanate; the blocked self-crosslinking single-component polyurethane adhesive obtained has low content of the blocking agent , which is favorable for improving the performance of adhesive films; at the same time, the adhesive has the advantages of high crosslinking density, higher mechanical strength and thermal stability, good storage stability and the like.
Description
Technical field
The present invention relates to polyurethane binder, especially relate to a kind of enclosed type self-crosslinking single component polyurethane binder and preparation method thereof.
Background technology
The blocked polyurethane tackiness agent is a kind of one-package adhesive, has preferably package stability.According to different encapsulants, impose different temperature, but its deblocking and while are reacted the formation macromolecular compound with the active hydrogen substance that contains that is present in the same system.
At present, following methods is adopted in the preparation of blocked polyurethane tackiness agent more:
(1) with line style polyether glycol or polyester polyol and two functionality isocyanate reactions, generate the polymers that gives take NCO as end group, then with the encapsulant sealing, mix with active hydrogen compounds again;
(2) polyfunctional group urethane crosslinks monomer is used the encapsulant complete closed in advance, then mix with active hydrogen compounds.
Method (1) generally is used for preparing the snappiness goods, and method (2) can be used to prepare the high rigidity goods.But the dissociateive NCO of the cross-linking monomer in the method (2) group must be all with the encapsulant sealing, and the encapsulant consumption is large, and solution is honored as a queen and can be remained in the glued membrane, and glue film performance is produced detrimentally affect.
Summary of the invention
Purpose of the present invention is exactly enclosed type self-crosslinking single component polyurethane binder that provides for the defective that overcomes above-mentioned prior art existence a kind of high mechanical strength and thermostability, low encapsulant consumption and preparation method thereof.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of enclosed type self-crosslinking single component polyurethane binder, the raw material of this tackiness agent comprises polyfunctionality isocyanic ester, encapsulant, polyvalent alcohol, it is characterized in that, described raw material consumption satisfies following formula:
[1-N
B/(cN
C)](a-1-N
B/N
A)＜[1/(c-1)]
Wherein, N
BThe mole number of expression encapsulant,
C represents the functionality of polyvalent alcohol,
N
CThe mole number of expression polyvalent alcohol,
A represents the functionality of polyfunctionality isocyanic ester,
N
AThe mole number of expression polyfunctionality isocyanic ester,
Described a, c are all 〉=2.
Described polyfunctionality isocyanic ester comprises tolylene diisocyanate (TDI) or TriMethylolPropane(TMP)-tolylene diisocyanate (TMP-TDI) affixture, and other polyfunctionality isocyanic ester.
Described encapsulant comprises phenol, hexanolactam, methyl aceto acetate or diethyl malonate.
Described polyvalent alcohol comprises micromolecular compound or low-molecular(weight)polymer, described micromolecular compound comprises glycol ether, glycerine, tetramethylolmethane, TriMethylolPropane(TMP), Viscotrol C or ricinoleate acid list glyceride, and described low-molecular(weight)polymer comprises that functionality is that polyethers or the functionality of 2-8 is the polyester of 2-3.
A kind of preparation method of enclosed type self-crosslinking single component polyurethane binder, it is characterized in that, at first that the NCO group of polyfunctionality isocyanic ester is partially enclosed with encapsulant, then remaining NCO group reacts with the part of hydroxyl of polyvalent alcohol again, finally make system keep the hydroxyl value that equates with sealing NCO base, the consumption of described polyfunctionality isocyanic ester, encapsulant, polyvalent alcohol satisfies following formula:
[1-N
B/(cN
C)](a-1-N
B/N
A)＜[1/(c-1)]
Wherein, N
BThe mole number of expression encapsulant,
C represents the functionality of polyvalent alcohol,
N
CThe mole number of expression polyvalent alcohol,
A represents the functionality of polyfunctionality isocyanic ester,
N
AThe mole number of expression polyfunctionality isocyanic ester,
Described a, c are all 〉=2.
Described polyfunctionality isocyanic ester comprises tolylene diisocyanate (TDI) or TriMethylolPropane(TMP)-tolylene diisocyanate (TMP-TDI) affixture, and other polyfunctionality isocyanic ester.
Described encapsulant comprises phenol, hexanolactam, methyl aceto acetate or diethyl malonate.
Described polyvalent alcohol comprises micromolecular compound or low-molecular(weight)polymer, described micromolecular compound comprises glycol ether, glycerine, tetramethylolmethane, TriMethylolPropane(TMP), Viscotrol C or ricinoleate acid list glyceride, and described low-molecular(weight)polymer comprises that functionality is that polyethers or the functionality of 2-8 is the polyester of 2-3.
Compared with prior art, the present invention adopts the encapsulant of small amount the polyfunctionality isocyanic ester to be carried out partially enclosed in advance, the content of encapsulant is lower in the enclosed type self-crosslinking single component polyurethane binder that obtains, be conducive to improve the performance of glued membrane, simultaneously tackiness agent of the present invention has high crosslink density, higher physical strength and thermostability, good advantages such as package stability.
Embodiment
The invention will be further described below in conjunction with specific embodiment.
The monomer of dead front type single-component polyurethane adhesive of the present invention has high functionality, and the encapsulant consumption is less than now methodical consumption, wherein:
| Component | Monomer | Functionality | Mole number | Reactive group |
| The polyfunctionality isocyanic ester | A | a(a≥2) | N A | The A base |
| Encapsulant | B | b(b＝1) | N B | The B base |
| Polyvalent alcohol | C | c(c≥2) | N C | The C base |
In order to guarantee that group A and group C complete reaction must guarantee to form complete network structure behind the deblocking
aN
A＝cN
C (1)
After monomer A was partially end-blocked by B, the free A radix that stays should equal
aN
A-N
B
After monomer C and the partially end-blocked monomer A complete reaction, the free C radix that stays should equal
N
B
In formulating of recipe of the present invention, determine N
BValue is to guarantee: gel does not occur and with minimum N in the reaction
B
If: P
A' level of response (the group number of reaction accounts for its total mark) of the partially end-blocked monomer A of representative
P
CRepresent the level of response of monomer C
When reaction is finished, excessive because of the C base, must have
P
A’＝1 (2)
P
C＝(cN
C-N
B)/(cN
C) (3)
According to the Flory gelation theory, if reaction does not produce gel, must have
P
A’P
C[(a-N
B/N
A)-1](c-1)＜1 (4)
(2), (3) substitution (4) are had:
[1-N
B/(cN
C)](a-1-N
B/N
A)＜[1/(c-1)] (5)
For selected system (a, c, N
A, N
CKnown), can calculate N thus
BSpan.
Embodiment 1
A kind of enclosed type self-crosslinking single component polyurethane binder, this tackiness agent comprise TDI (monomer A, functionality a=2), encapsulant diethyl malonate (monomers B, functionality b=1), polyol E 310 (monomer C, functionality c=3), take monomer A as benchmark, make N
A=1mol knows N by formula (1)
C=2/3mol, substitution formula (5):
(1-N
B/2)(1-N
B)＜1/2
(1-N
B)
2+2×1/2(1-N
B)+(1/2)
2＜[1+(1/2)
2]
[(1-N
B)+1/2]
2＜[1+(1/2)
2]
: N
B〉=0.38mol
Embodiment 2
A kind of enclosed type self-crosslinking single component polyurethane binder, this tackiness agent comprise TMP-TDI affixture (monomer A, functionality a=3), encapsulant phenol (monomers B, functionality b=1), polyol E 310 (monomer C, functionality c=3), take monomer A as benchmark, make N
A=1mol knows N by formula (1)
C=1mol, substitution formula (5):
(1-N
B/3)(2-N
B)＜1/2
(2-N
B)
2+2×1/2(2-N
B)+(1/2)
2＜[3/2+(1/2)
2]
[(2-N
B)+1/2]
2＜[3/2+(1/2)
2]
: N
B＞1.15mol
Embodiment 3
In the present embodiment: the polyfunctionality isocyanic ester adopts the TDI (functionality 2.0) of Shanghai reagent one factory;
Encapsulant adopts the diethyl malonate of Tianjin Chemical Reagents Factory No.1;
Polyvalent alcohol adopts homemade ricinoleate acid list glyceride (average functionality 2.9).
A kind of preparation method of enclosed type self-crosslinking single component polyurethane binder, the method may further comprise the steps:
(1) ricinoleate acid list glyceride is synthetic: take by weighing glycerine and Viscotrol C, the two mol ratio is 2: 1, pours in the three-necked bottle, the PbO that adds glycerine weight 0.8% is catalyzer, and logical nitrogen is opened stirring, be warming up to simultaneously 220 ℃ of reactions 1 hour, get ricinoleate acid list glyceride;
(2) polyisocyanates is partially enclosed: take by weighing TDI (1.5mol, approximately 261g) and encapsulant diethyl malonate (1.0mol, approximately 168g), adding in advance 0.2% sodium ethylate in the diethyl malonate is catalyzer; First TDI is dropped into reaction flask, start stirring, then drip diethyl malonate-alcohol sodium solution, exothermic heat of reaction about automatic heating to 70 ℃, approximately dropwised in 40 minutes, was warming up to 90 ℃, reacted approximately and finished in 2 hours;
(3) polyreaction: the partially enclosed polyisocyanates that step (2) is obtained slowly adds in batches ricinoleate acid direactive glyceride (1.0mol is housed, about 380g) in the reaction flask, 70-80 ℃ of control temperature of reaction, treat that the dissociateive NCO reaction is complete, finish reaction, get enclosed type self-crosslinking single component polyurethane binder.
In the present embodiment, only need the 1mol encapsulant, if adopt prior art then to need the 3mol encapsulant.The tackiness agent of above-mentioned preparation has good package stability, and self-crosslinkable solidifies under 130-140 ℃ of condition.
Claims (2)
1. enclosed type self-crosslinking single component polyurethane binder, the raw material of this tackiness agent comprises polyfunctionality isocyanic ester, encapsulant, polyvalent alcohol, it is characterized in that, described raw material consumption satisfies following formula:
[1- N
B/（cN
C）]（a-1- N
B/ N
A）﹤[1/（c-1）]
Wherein, N
BThe mole number of expression encapsulant,
C represents the functionality of polyvalent alcohol,
N
CThe mole number of expression polyvalent alcohol,
A represents the functionality of polyfunctionality isocyanic ester,
N
AThe mole number of expression polyfunctionality isocyanic ester,
Described a, c are all 〉=2;
Described polyfunctionality isocyanic ester comprises tolylene diisocyanate (TDI) or TriMethylolPropane(TMP)-tolylene diisocyanate (TMP-TDI) affixture;
Described encapsulant comprises phenol, hexanolactam, methyl aceto acetate or diethyl malonate;
Described polyvalent alcohol comprises micromolecular compound or low-molecular(weight)polymer, described micromolecular compound comprises glycol ether, glycerine, tetramethylolmethane, TriMethylolPropane(TMP), Viscotrol C or ricinoleate acid list glyceride, and described low-molecular(weight)polymer comprises that functionality is that polyethers or the functionality of 2-8 is the polyester of 2-3.
2. the preparation method of an enclosed type self-crosslinking single component polyurethane binder, it is characterized in that, at first that the NCO group of polyfunctionality isocyanic ester is partially enclosed with encapsulant, then remaining NCO group reacts with the part of hydroxyl of polyvalent alcohol again, finally make system keep the hydroxyl value that equates with sealing NCO base, the consumption of described polyfunctionality isocyanic ester, encapsulant, polyvalent alcohol satisfies following formula:
[1- N
B/（cN
C）]（a-1- N
B/ N
A）﹤[1/（c-1）]
Wherein, N
BThe mole number of expression encapsulant,
C represents the functionality of polyvalent alcohol,
N
CThe mole number of expression polyvalent alcohol,
A represents the functionality of polyfunctionality isocyanic ester,
N
AThe mole number of expression polyfunctionality isocyanic ester,
Described a, c are all 〉=2;
Described polyfunctionality isocyanic ester comprises tolylene diisocyanate (TDI) or TriMethylolPropane(TMP)-tolylene diisocyanate (TMP-TDI) affixture;
Described encapsulant comprises phenol, hexanolactam, methyl aceto acetate or diethyl malonate;
Described polyvalent alcohol comprises micromolecular compound or low-molecular(weight)polymer, described micromolecular compound comprises glycol ether, glycerine, tetramethylolmethane, TriMethylolPropane(TMP), Viscotrol C or ricinoleate acid list glyceride, and described low-molecular(weight)polymer comprises that functionality is that polyethers or the functionality of 2-8 is the polyester of 2-3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810033516 CN101503610B (en) | 2008-02-04 | 2008-02-04 | Enclosed type self-crosslinking single component polyurethane binder and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810033516 CN101503610B (en) | 2008-02-04 | 2008-02-04 | Enclosed type self-crosslinking single component polyurethane binder and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101503610A CN101503610A (en) | 2009-08-12 |
| CN101503610B true CN101503610B (en) | 2013-04-03 |
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ID=40975995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200810033516 Active CN101503610B (en) | 2008-02-04 | 2008-02-04 | Enclosed type self-crosslinking single component polyurethane binder and preparation thereof |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20230151135A1 (en) * | 2016-10-18 | 2023-05-18 | Covestro Deutschland Ag | Production of plastics by catalytic crosslinking of blocked polyisocyanates |
| CN108687903A (en) * | 2018-04-24 | 2018-10-23 | 广州精点高分子材料制品有限公司 | A kind of application method based on closed NCO group ceramics wood |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1796432A (en) * | 2004-12-30 | 2006-07-05 | 上海理日化工新材料有限公司 | Polyesterglycol, adhesive of polyurethane and decorating plate of aluminum with high light film being covered |
| CN1865328A (en) * | 2006-04-27 | 2006-11-22 | 中国科学院广州化学研究所 | Water dispersible end capping diisocyanate cross-linking agent and its preparation method |
| CN101469259A (en) * | 2007-12-27 | 2009-07-01 | 上海轻工业研究所有限公司 | Polyurethane reactive hot melt structure adhensive |
-
2008
- 2008-02-04 CN CN 200810033516 patent/CN101503610B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1796432A (en) * | 2004-12-30 | 2006-07-05 | 上海理日化工新材料有限公司 | Polyesterglycol, adhesive of polyurethane and decorating plate of aluminum with high light film being covered |
| CN1865328A (en) * | 2006-04-27 | 2006-11-22 | 中国科学院广州化学研究所 | Water dispersible end capping diisocyanate cross-linking agent and its preparation method |
| CN101469259A (en) * | 2007-12-27 | 2009-07-01 | 上海轻工业研究所有限公司 | Polyurethane reactive hot melt structure adhensive |
Non-Patent Citations (2)
| Title |
|---|
| "TDI-TMP加成物合成工艺的研究";彭红为等;《聚氨酯工业》;20001231;第15卷(第2期);第25-28页 * |
| 彭红为等."TDI-TMP加成物合成工艺的研究".《聚氨酯工业》.2000,第15卷(第2期),第25-28页. |
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| CN101503610A (en) | 2009-08-12 |
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