CN106046286B - A kind of polyurethane and preparation method thereof containing naphthalene ring - Google Patents
A kind of polyurethane and preparation method thereof containing naphthalene ring Download PDFInfo
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- CN106046286B CN106046286B CN201610375491.7A CN201610375491A CN106046286B CN 106046286 B CN106046286 B CN 106046286B CN 201610375491 A CN201610375491 A CN 201610375491A CN 106046286 B CN106046286 B CN 106046286B
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- polyurethane
- naphthalene ring
- diisocyanate
- containing naphthalene
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- 0 OCCCCC(*c1cccc2c(*C(*CCCO)=O)cccc12)=O Chemical compound OCCCCC(*c1cccc2c(*C(*CCCO)=O)cccc12)=O 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to a kind of polyurethane containing naphthalene ring, with 1,5 naphthalene diisocyanates, diisocyanate, hydroxylamine and oligomer dihydric alcohol etc. are raw material, the polyurethane containing naphthalene ring being prepared is increased dramatically compared to mechanical performances such as the elasticity of traditional elastomeric material, modulus, intensity and elongation at breaks, has potential application in the fields such as machinery and chemical industry.The invention further relates to preparation methods, have simple, easy to implement and control and production efficiency height.
Description
Technical field
The present invention relates to polyurethane fields, and in particular to a kind of polyurethane and preparation method thereof containing naphthalene ring.
Background technology
Polyurethane material is the current best thermal insulation material of performance in the world.Main chain constitutional repeating unit Han-NHCOO-
A kind of polymer.It is polymerized with hydroxy compounds by isocyanates (monomer).Due to containing highly polar carbamate groups, no
It is dissolved in non-polar group, there is good oil resistivity, toughness, wearability, resistance to ag(e)ing and adhesiveness.It can be made with different material
Adapt to the material of wide temperature range (- 50~150 DEG C), including elastomer, thermoplastic resin and thermosetting resin.Under high temperature not
Hydrolysis, also not alkali-proof medium.
Common monomer such as toluene di-isocyanate(TDI), diisocyanate diphenyl-methane etc..3 classes of polyalcohol point：It is simple polynary
Alcohol (ethylene glycol, glycerine etc.)；Polyester oligomer containing terminal hydroxyl, for preparing polyester polyurethane；Containing terminal hydroxyl
Polyether oligomers, for preparing polyether polyurethane.Polymerization is different with material character.It is first prepared when synthetic elastomer low
Molecular weight dihydric alcohol, then reacted with excessive aromatic isocyanate, the prepolymer that isocyanates is end group is generated, then expand with butanediol
Chain obtains thermoplastic elastomer；If being crosslinked with aromatic diamine chain extension and further, casting type elastomer is obtained.Prepolymer hydrazine or
Diamine chain extension, obtains elastomer；Excessively more performed polymer mixes isocyanates with catalyst, foaming agent, can directly obtain
To rigid foam.Such as by monomer, polyethers, water, catalyst mixing, single step reaction can be obtained flex foam.It is single
Body reacts in the solution with polyalcohol, and coating can be obtained；Adhesive then with polyisocynate monomer and low molecular weight polyester or gathers
Ether is mixed and is reacted when in use.
Currently, polyurethane material is synthesized by diisocyanate with oligomer polyol two-step method, generated by microphase-separated
Special construction assign the preferable mechanical performance of polyurethane, but since rigid chain segment hydrogen bond action deficiency frequently results in polyurethane
The problems such as mechanical performance declines.
Invention content
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of polyurethane and its system containing naphthalene ring
Preparation Method.The polyurethane containing naphthalene ring being prepared compared to traditional elastomeric material, elasticity, modulus, intensity with
And the mechanical performances such as elongation at break are increased dramatically, and have potential application in fields such as machinery, chemical industry.
Technical solution provided by the present invention is：A kind of polyurethane containing naphthalene ring, the structure of the polyurethane
Formula is as follows：
In formula (I), n is that 1~5, m is 1~30；
The polyurethane is obtained by the reaction by following structural formula (II), (III) and (IV)：
HO-R1-OH (Ⅱ)；
O=C=N-R2- N=C=O (III)；
The formula (II) is oligomer dihydric alcohol；The formula (III) is diisocyanate；The formula (IV) is by 1,5
Naphthalene diisocyanate is obtained by the reaction with hydroxylamine.
In above-mentioned technical proposal, the polyurethane containing naphthalene ring is prepared by conventional organic micromolecule compound, energy
All kinds of polyurethane synthesis are enough widely used in, the mechanical performance of polyurethane material is substantially improved, can be widely applied to chemical industry, machinery etc.
Field.Hydroxy-end capped naphthalene nucleus chain extender directly reacts generation by 1,5- naphthalene diisocyanates and hydroxylamine, utilizes existingization
Construction equipment can generate on a large scale, have the advantages that reactivity is high, and reaction condition is mild, and yield is high.Naphthalene nucleus is introduced poly-
In urethane strand, due to the difference of cloud density, which can interact that strand is made to generate folding.
Preferably, the hydroxylamine be ethanol amine, isopropanolamine, n-propanolamine, diglycolamine, D- aminopropanols,
One kind or several in the different bright amine alcohol of hydroxyl acetamide, L-, 4- amino-n-butyl alcohol, 5- amino -1- amylalcohols or 6- amino -1- hexanols
Kind.
Preferably, the oligomer dihydric alcohol is polyester diol or polyether Glycols.
Further preferably, the polyether Glycols are polytetrahydrofuran ether glycol.The polytetrahydrofuran ether glycol
For PolyTHF 250, PolyTHF 650, PolyTHF 1000, PolyTHF 2000 or PolyTHF 3000.
Preferably, the diisocyanate is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, 1,5- naphthalenes
Diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, benzene dimethylene diisocyanate or to benzene two
One or more of isocyanates.
The present invention also provides a kind of preparation methods such as the above-mentioned polyurethane containing naphthalene ring, including following step：
1) in polar solvent, 1,5- naphthalene diisocyanates is added and are reacted with hydroxylamine, obtain hydroxy-end capped naphthalene nucleus and expand
Chain agent；
2) oligomer dihydric alcohol and diisocyanate are added in polar solvent, under the action of catalyst, urethane occur
Change reaction, obtains polyurethane prepolymer；
3) determination step 2) in polyurethane prepolymer-content of NCO group, hydroxy-end capped naphthalene nucleus chain extender is added
It is warming up to 70~90 DEG C of 2~3h of reaction；
4) reaction system in step 3) is added in methanol, product is precipitated to get the poly- ammonia containing naphthalene ring in filtering
Ester.
Above-mentioned preparation method, preparation method is simple, and easy to implement and control, production efficiency is higher, equipment is simple.
Preferably, hydroxylamine is ethanol amine, isopropanolamine, n-propanolamine, diglycolamine, D- ammonia in the step 1)
One in the different bright amine alcohol of base propyl alcohol, hydroxyl acetamide, L-, 4- amino-n-butyl alcohol, 5- amino -1- amylalcohols or 6- amino -1- hexanols
Kind is several.
Preferably, the polar solvent is n,N-Dimethylformamide, n,N-dimethylacetamide or dimethyl sulfoxide.
Preferably, catalyst is tertiary amine or organotin in the step 2).Further preferably, the catalyst is
Dibutyltin dilaurate catalyst.
Preferably, the molar ratio of oligomer dihydric alcohol and diisocyanate is 1 in the step 2):2~2.1.
Preferably, hydroxy-end capped naphthalene nucleus chain extender is added in the step 3) and the molar ratio of-NCO group is
0.5~0.55.
Preferably, the method for the content of measurement-NCO group detects for infrared spectrum in the step 3).
Compared with the existing technology, beneficial effects of the present invention are embodied in：Hydroxy-end capped naphthalene nucleus chain extender and contain naphthalene nucleus
The preparation method of the polyurethane of structure is relatively simple, and the mechanical performance of polymer material obtains substantially compared with conventional urethane material
It is promoted, can be widely applied to the related fields such as chemical industry, machinery.
Description of the drawings
Fig. 1 is the stress-strain diagram of the polyurethane containing naphthalene ring in embodiment 1；
Fig. 2 is the nuclear magnetic resonance spectroscopy of the polyurethane containing naphthalene ring in embodiment 2.
Specific implementation mode
With reference to embodiment, the present invention is further explained.
Nuclear magnetic resonance spectroscopy in embodiment1H-NMR uses the III type spectroscopes of 400AVANCE of Brooker company (Bruker)
(Spectrometer) it measures, 400MHz, solvent is deuterated dimethyl sulfoxide.
Embodiment 1
By 10g 1,5- naphthalene diisocyanates, 5.81g ethanol amines are added in 100ml n,N-Dimethylformamide, under room temperature
It is persistently stirred to react 0.5h, is filtered, drying obtains hydroxy-end capped naphthalene nucleus chain extender.
It is characterized by nuclear magnetic resonance spectroscopy, nuclear magnetic data is as follows：
δ/ppm=3.16-3.25 (m, 2H), 3.45-3.58 (m, 2H), 4.76-4.84 (m, 2H), 6.71-6.79 (m,
2H), 7.39-7.48 (m, 2H), 7.71-7.77 (d, J=8.55Hz, 2H), 7.99-8.05 (d, J=7.77Hz, 2H), 8.55
(s,2H).
Obtained product such as formula I：
By 4g polytetrahydrofuran ether glycol (molecular weight 650), 30g N, N- is added in 2.07g hexamethylene diisocyanates
In dimethylformamide, and 3-5 drop dibutyltin dilaurate catalysts are added dropwise, react 4h at 65 DEG C.
The content of-NCO in above-mentioned system is measured, the hydroxy-end capped naphthalene nucleus chain extender of the amount 1/2 of addition-NCO substances will
Temperature is increased to 80 DEG C, the reaction was continued 2h.
Above-mentioned reactant is added in methanol, so that product is precipitated, filters out product, be dissolved in appropriate N, N- dimethyl methyls
In amide, solution is poured into mold, drying and moulding obtains the film of polyether polyols containing naphthalene ring.
The ess-strain performance of the polyurethane containing naphthalene ring is measured, the results are shown in Figure 1.
Embodiment 2
By 10g 1,5- naphthalene diisocyanates, 7.14g ethanol amines are added in 100ml n,N-dimethylacetamide, under room temperature
It is persistently stirred to react 0.5h, is filtered, drying obtains hydroxy-end capped naphthalene nucleus chain extender.
Obtained product such as formula II
By 6.2g polytetrahydrofuran ether glycol (molecular weight 1000), 30g is added in 2.07g hexamethylene diisocyanates
In n,N-Dimethylformamide, and 3-5 drop dibutyltin dilaurate catalysts are added dropwise, react 4h at 65 DEG C.
The content of-NCO in above-mentioned system is measured, the hydroxy-end capped naphthalene nucleus chain extender of the amount 1/2 of addition-NCO substances will
Temperature is increased to 80 DEG C, the reaction was continued 2h.
Above-mentioned reactant is added in methanol, so that product is precipitated, filters out product, be dissolved in appropriate N.N- dimethyl methyls
In amide, solution is poured into mold, drying and moulding obtains the film of polyether polyols containing naphthalene ring.
It is characterized by nuclear magnetic resonance spectroscopy, the nuclear magnetic data of the polyurethane containing naphthalene ring is as shown in Figure 2.
Embodiment 3
By 10g 1,5- naphthalene diisocyanates, 5.81g ethanol amines are added in 100ml dimethyl sulfoxides, are persistently stirred under room temperature
0.5h is reacted, suction filtration, drying obtain hydroxy-end capped naphthalene nucleus chain extender, such as formula III：
By 12.3g polytetrahydrofuran ether glycol (molecular weight 2000), 30g is added in 2.73g isophorone diisocyanate
In dimethyl sulfoxide, and 3-5 drop dibutyltin dilaurate catalysts are added dropwise, react 4h at 65 DEG C.
The content of-NCO in above-mentioned system is measured, the hydroxy-end capped naphthalene nucleus chain extender of the amount 1/2 of addition-NCO substances will
Temperature is increased to 80 DEG C, the reaction was continued 2h.
Above-mentioned reactant is added in methanol, so that product is precipitated, filters out product, be dissolved in appropriate N, N- dimethyl methyls
In amide, solution is poured into mold, drying and moulding obtains the film of polyether polyols containing naphthalene ring.
Performance test
The polyurethane containing naphthalene ring being prepared in embodiment 1, measures its elasticity modulus, tensile stress, fracture
Elongation, response rate and molecular weight, the results are shown in table below.
Above-mentioned is to elaborate in conjunction with the embodiments to the present invention, but embodiments of the present invention are not by above-mentioned implementation
Example limitation, it is other it is any under patent core guiding theory of the present invention made by change, replace, combination simplify etc. be included in
Within the protection domain of patent of the present invention.
Claims (10)
1. a kind of polyurethane containing naphthalene ring, which is characterized in that the structural formula of the polyurethane is as follows：
In formula (I), n is that 1~5, m is 1~30；
The polyurethane is obtained by the reaction by following structural formula (II), (III) and (IV)：
HO-R1-OH (Ⅱ)；
O=C=N-R2- N=C=O (III)；
The formula (II) is oligomer dihydric alcohol；The formula (III) is diisocyanate；The formula (IV) is by 1,5 naphthalenes two
Isocyanates is obtained by the reaction with hydroxylamine.
2. the polyurethane according to claim 1 containing naphthalene ring, which is characterized in that the hydroxylamine is ethyl alcohol
The different bright amine alcohol of amine, isopropanolamine, n-propanolamine, diglycolamine, D- aminopropanols, hydroxyl acetamide, L-, 4- amino-n-butyl alcohol,
One or more of 5- amino -1- amylalcohols or 6- amino -1- hexanols.
3. the polyurethane according to claim 1 containing naphthalene ring, which is characterized in that the oligomer dihydric alcohol is
Polyester diol or polyether Glycols.
4. the polyurethane according to claim 1 containing naphthalene ring, which is characterized in that the diisocyanate is first
Phenylene diisocyanate, methyl diphenylene diisocyanate, 1,5- naphthalene diisocyanates, hexamethylene diisocyanate, different Fo Er
One or more of ketone diisocyanate, benzene dimethylene diisocyanate or paraphenylene diisocyanate.
5. a kind of preparation method of polyurethane containing naphthalene ring as described in Claims 1 to 4 is any, which is characterized in that
Including following step：
1) in polar solvent, 1,5- naphthalene diisocyanates is added and are reacted with hydroxylamine, obtain hydroxy-end capped naphthalene nucleus chain extender；
2) oligomer dihydric alcohol and diisocyanate are added in polar solvent, under the action of catalyst, it is anti-that urethaneization occur
It answers, obtains polyurethane prepolymer；
3) determination step 2) in polyurethane prepolymer-content of NCO group, hydroxy-end capped naphthalene nucleus chain extender heating is added
To 70~90 DEG C of 2~3h of reaction；
4) reaction system in step 3) is added in methanol, product is precipitated to get the polyurethane containing naphthalene ring in filtering.
6. the preparation method of the polyurethane according to claim 5 containing naphthalene ring, which is characterized in that the step
1) hydroxylamine is ethanol amine, isopropanolamine, n-propanolamine, diglycolamine, D- aminopropanols, hydroxyl acetamide, the different bright amine of L- in
One or more of alcohol, 4- amino-n-butyl alcohol, 5- amino -1- amylalcohols or 6- amino -1- hexanols.
7. the preparation method of the polyurethane according to claim 5 containing naphthalene ring, which is characterized in that the step
2) catalyst is tertiary amine or organotin in.
8. the preparation method of the polyurethane according to claim 5 containing naphthalene ring, which is characterized in that the step
2) molar ratio of oligomer dihydric alcohol and diisocyanate is 1 in:2~2.1.
9. the preparation method of the polyurethane according to claim 8 containing naphthalene ring, which is characterized in that the step
3) molar ratio that hydroxy-end capped naphthalene nucleus chain extender and-NCO group are added in is 0.5~0.55.
10. the preparation method of the polyurethane according to claim 5 containing naphthalene ring, which is characterized in that the step
It is rapid 3) in measurement-NCO group content method be infrared spectrum detection.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6162863A (en) * | 1997-12-04 | 2000-12-19 | Henkel Kommanditgesellschaft Auf Aktien | Waterborne polyurethanes with urea-urethane linkages |
| CN102432818A (en) * | 2011-11-18 | 2012-05-02 | 上海珀理玫化学科技有限公司 | Preparation method of1,5-naphthalene diisocyanate-based polyurethane microcellular elastomer |
-
2016
- 2016-05-30 CN CN201610375491.7A patent/CN106046286B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6162863A (en) * | 1997-12-04 | 2000-12-19 | Henkel Kommanditgesellschaft Auf Aktien | Waterborne polyurethanes with urea-urethane linkages |
| CN102432818A (en) * | 2011-11-18 | 2012-05-02 | 上海珀理玫化学科技有限公司 | Preparation method of1,5-naphthalene diisocyanate-based polyurethane microcellular elastomer |
Non-Patent Citations (2)
| Title |
|---|
| NDI型聚氨酯弹性体的合成与其耐热性能研究;甄建军等;《工程塑料应用》;20061231;第34卷(第11期);第61-63页 * |
| NDI型聚氨酯弹性体的氢键研究;余成科等;《北京化工大学学报（自然科学版）》;20121231;第39卷(第6期);第52-57页 * |
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