CN103289054A - Xylitol aromatic polyurethane - Google Patents
Xylitol aromatic polyurethane Download PDFInfo
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- CN103289054A CN103289054A CN2013102066390A CN201310206639A CN103289054A CN 103289054 A CN103289054 A CN 103289054A CN 2013102066390 A CN2013102066390 A CN 2013102066390A CN 201310206639 A CN201310206639 A CN 201310206639A CN 103289054 A CN103289054 A CN 103289054A
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- xylitol
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Abstract
The invention provides xylitol aromatic polyurethane which is characterized in that the xylitol aromatic polyurethane is a block polymer formed by copolymerizing soft-segment xylitol and hard-segment methylbenzene-2,4-diisocyanate, and the structural formula is shown in the specification, wherein in the specification, the soft segment and the hard segment are respectively shown; and the xylitol aromatic polyurethane is prepared from xylitol, polybasic isocyanate, a catalyst, a chain extender and a solvent. The xylitol aromatic polyurethane provided by the invention is prepared by a solution polymerization method. According to the method provided by the invention, the equipment is simple, and the synthesis technology is easy to control. The xylitol aromatic polyurethane provided by the invention can be used as a light-transmitting material, an ultraviolet-resistant material and a chemical corrosion-resistant material; particularly, the glass transition temperature is as high as 171.6 DEG C which is 35.46-120.13% higher than common polyurethane resin; and the xylitol aromatic polyurethane can be used as a high temperature-resistant new material.
Description
Technical field
The present invention relates to a kind of Xylitol fragrant urethane.
Background technology
(Polyurethane PU) has the performance of many excellences and good processing characteristics as a class synthesized polymer material to urethane, is widely used in fields such as automobile, building, machinery, light industry, food and medical treatment.But common resistant polyurethane is hot poor, it is generally acknowledged, urethane resin is at the life-time service of energy below 80 ℃, and the short-term use temperature is no more than 130 ℃.Along with the continuous expansion that material is used, the research and development of high performance polyurethane more and more are subjected to people's attention.Particularly in recent years, along with the fast development of industries such as building energy conservation, automotive industry, high ferro, subway, household electrical appliances, new forms of energy and environmental protection, greatly spurred the demand of polyurethane products, resistant to elevated temperatures polyurethane material is to be badly in need of in the industry.
Summary of the invention
In order to solve the shortcoming of existing material, the invention provides a kind of Xylitol fragrant urethane, especially obtained a kind of resistant to elevated temperatures Xylitol fragrant urethane.
The invention provides a kind of Xylitol fragrant urethane, it is by soft section Xylitol and hard section Toluene-2,4-diisocyanate, the block polymer that the copolymerization of 4-vulcabond forms, and its structural formula is as follows:
Wherein,
Be soft section,
Be hard section.
The invention provides a kind of Xylitol fragrant polyurethane preparation method, its step and condition are as follows:
(1) pre-polymerization operation: by proportioning, earlier solvent is joined in the reactor, reaction system is vacuumized processing, under nitrogen protection, add polyvalent alcohol and multicomponent isocyanate, under room temperature, stir and react 15 ~ 60min, then, add catalyzer in the reaction system that continues to stir, oil bath is warming up to 40 ~ 90 ℃, reaction 3 ~ 5h, detect in the solution-content of NCO with the Di-n-Butyl Amine method, when the content of-NCO reaches 15 ~ 18%, enter the chain extension operation;
(2) chain extension operation: by proportioning: the quality g of polyvalent alcohol, multicomponent isocyanate, catalyzer, chainextender is 50.00:95-175:0.03-0.05:16-28:1270-1470 with the ratio of the volume mL of solvent, in the system of step (1), add chainextender, continue reaction 10 ~ 60min, removal of solvent under reduced pressure obtains transparent viscous solution; By prolonging the stream method transparent viscous solution is poured in the mould, solidifies 24 ~ 96h under the condition of room temperature, the demoulding makes Xylitol fragrant urethane;
Described polyvalent alcohol is Xylitol; Isocyanic ester is isophorone diisocyanate, Toluene-2,4-diisocyanate, 4-vulcabond or 4,4-diphenylmethanediisocyanate; Catalyzer is stannous octoate or dibutyl tin laurate; Chainextender is ethylene glycol, 1,4-butyleneglycol, 1,2-propylene glycol, 1, the mixture of a kind of in the 6-hexylene glycol or their any ratio; Solvent is the mixed solvent of tetrahydrofuran (THF), acetone, N, dinethylformamide, ethyl acetate or their any ratio;
Beneficial effect:A kind of Xylitol fragrant urethane of the present invention, it is by soft section Xylitol and hard section Toluene-2,4-diisocyanate, the block polymer that the copolymerization of 4-vulcabond forms.This Xylitol fragrant urethane, (1) has light transmission preferably, can be used as light transmissive material; (2) ultraviolet resistance irradiation can be used as anti-uv materials; (3) resistance to chemical attack; (4) common urethane generally can use below 80 ℃, and the use temperature of minority urethane is no more than 130 ℃.Xylitol fragrant polyurethane glass temperature of the present invention exceeds 35.46-120.13% up to 171.6 ℃ than common urethane resin, and it can be used as resistant to elevated temperatures novel material.The equipment of the preparation of the Xylitol fragrant urethane that the present invention obtains is simple, and synthesis technique is easy to control.
Description of drawings
Fig. 1 is the Xylitol fragrant urethane that obtains of the present invention and Fourier transform far infrared (FTIR) abosrption spectrogram of Xylitol.
Fig. 2 is the Xylitol fragrant urethane that obtains of the present invention and the X-ray diffraction spectrogram of Xylitol.
Fig. 3 is the DSC curve spectrogram of the Xylitol fragrant urethane that obtains of the present invention.
Fig. 4 is the thermogravimetric curve spectrogram of the Xylitol fragrant urethane that obtains of the present invention.
Embodiment
Make further detailed explanation below by the present invention of embodiment, but content not thereby limiting the invention.
Embodiment 1A kind of Xylitol fragrant urethane, it is by soft section Xylitol and hard section Toluene-2,4-diisocyanate, the block polymer that the copolymerization of 4-vulcabond forms, its structural formula is as follows:
Wherein,
Be soft section,
Be hard section.
A kind of Xylitol fragrant polyurethane preparation method, step and condition are as follows:
Raw materials usedly see Table 1;
(1) pre-polymerization operation: earlier acetone is joined in the reactor, reaction system is vacuumized processing, under nitrogen protection, add Xylitol and isophorone diisocyanate, under room temperature, stir and reaction 15min, then, in the reaction system that continues to stir, add the inferior tin of octoate catalyst, oil bath is warming up to 40 ℃, and reaction 3h detects in the solution-content of NCO with the Di-n-Butyl Amine method, when the content of-NCO reaches 15 ~ 18%, enter the chain extension operation;
(2) chain extension operation: in the system of step (1), add chainextender 1, the 4-butyleneglycol, continue reaction 10min, acetone solvent is removed in decompression, obtain transparent viscous solution, by prolonging the stream method transparent viscous solution is poured in the mould, under the condition of room temperature, solidify 24h, the demoulding makes Xylitol fragrant urethane.
Embodiment 2A kind of Xylitol fragrant urethane, a kind of Xylitol fragrant urethane, it is by soft section Xylitol and hard section Toluene-2,4-diisocyanate, the block polymer that the copolymerization of 4-vulcabond forms, its structural formula such as embodiment 1.
A kind of Xylitol fragrant polyurethane preparation method, step and condition are as follows:
Raw materials usedly see Table 2;
(1) pre-polymerization operation: earlier tetrahydrofuran (THF) is joined in the reactor; reaction system is vacuumized processing, under nitrogen protection, add Xylitol and Toluene-2,4-diisocyanate, 4-vulcabond; under room temperature, stir and reaction 60min; then, add the catalyzer dibutyl tin laurate in the reaction system that continues to stir, oil bath is warming up to 90 ℃; reaction 5h; detect in the solution-content of NCO with the Di-n-Butyl Amine method, when the content of-NCO reaches 10 ~ 15%, enter the chain extension operation.
(2) chain extension operation: in the system of step (1), add chainextender ethylene glycol, continue reaction 60min, tetrahydrofuran solvent is removed in decompression, obtain transparent viscous solution, by prolonging the stream method transparent viscous solution is poured in the mould, solidify 96h under the condition of room temperature, the demoulding makes Xylitol fragrant urethane.
Structure and the performance characterization of the Xylitol fragrant polyurethane material that embodiment 2 prepares.
Toluene-2,4-diisocyanate, methyl contraposition in the 4-vulcabond-activity of NCO group be higher than far away its ortho position-activity of NCO group, when adding Toluene-2,4-diisocyanate, during the 4-vulcabond, contraposition-a terminal hydroxy group reaction of NCO and Xylitol generates end band-NCO base, the polyhydric active intermediate of the other end band, the rising temperature and under the effect that adds catalyzer their further polymerizations generate low-molecular-weight polymkeric substance, and under the condition of ethylene glycol as chainextender, oligomerization product polymerization gradually generates Xylitol fragrant urethane.
Accompanying drawing 1 is Fourier transform far infrared (FTIR) abosrption spectrogram of Xylitol (a) and Xylitol fragrant urethane (b), and the b infrared spectrum as can be known from accompanying drawing 1: at 1724cm
-1Stronger absorption peak occurs and be in the system-NCO and-carbamate groups that the OH reaction generates in-C=O(ammonia ester carbonyl group) the stretching vibration absorption peak, illustrate-NHCO and-reaction taken place in OH, namely Xylitol has participated in reacting in the main chain that is introduced in Xylitol fragrant polyurethane molecular; At 3425.79cm
-1And 3367cm
-1The strong absorption peak that occurs is the stretching vibration absorption peak of hydroxyl, compares with the infared spectrum of Xylitol, at 3393.8cm
-1Absorption peak obviously weaken, illustrate that the hydroxyl on the Xylitol has participated in reaction, further specify in the successful molecular chain of receiving sample of Xylitol.2270cm
-1Near-completely dissolve of NCO absorption characteristic peak, show there is not free-NCO group in the polymkeric substance that Toluene-2,4-diisocyanate is described, the 4-vulcabond participates in reaction fully.
Adopt X-ray diffractometer (XRD) that the crystallization behavior of Xylitol and Xylitol fragrant urethane is analyzed, the result as shown in Figure 2.A is the X-ray diffraction spectrogram of Xylitol among the figure, the peak type of Xylitol diffraction peak is sharp-pointed as can be known by collection of illustrative plates, show that degree of crystallinity is very high, and the X-ray diffraction image (b) of Xylitol fragrant urethane only the diffuse scattering peak occurs near 2 θ=20.94 °, belong to amorphous polymer, this may be that molecule is in lack of alignment because highly branched structure and the unsymmetrical structure of synthetic Xylitol fragrant urethane cause its symmetry and regularity to reduce.This also illustrates Xylitol complete reaction substantially, simultaneously, because the secondary hydroxyl at Xylitol two ends has participated in reaction, make hydrogen bond action between Xylitol fragrant polyurethane molecular be weaker than the hydrogen bond action between xylitol molecules far away, this makes that also Xylitol fragrant urethane is non-crystalline state, has confirmed that further Xylitol has been incorporated in the molecular chain of Xylitol fragrant urethane as the poly-hydroxy raw material.
Adopt differential scanning calorimeter that the thermal characteristics of Xylitol and Xylitol fragrant urethane is analyzed, accompanying drawing 3 is Xylitol fragrant urethane DSC curve.As can be seen from the figure, on its DSC curve, only exist a more weak ladder to transform corresponding second-order transition temperature, the tangible melting hump of none, the second-order transition temperature of Xylitol fragrant urethane is 171.60 ℃, illustrate that urethane resin can use below 170 ℃, this use temperature than general urethane resin (80～100 ℃) is high.This is owing to contain the benzene ring structure of rigidity on the main chain, and molecular chain may present highly branched, cause the mobility of segment to descend, make that the second-order transition temperature of Xylitol fragrant urethane is higher, not seeing among the figure has melting peak, shows that polymkeric substance is non-crystalline state, illustrates that soft section phase is non-crystalline state mutually with hard section, the XRD curve of polymkeric substance shows as single diffuse maximum in the accompanying drawing 2, has further proved this point.This may be the motion that the phenyl ring of rigidity in the Xylitol fragrant polyurethane molecular has limited polymer segment, thereby hinders polymer crystallization.In this experiment, the molecular weight of used Xylitol is 152, pertinent literature research is pointed out, the molecular-weight average of polyvalent alcohol was greater than 2000 o'clock, soft section just meeting crystallization, thereby the flexible polyurethane section is in amorphous state mutually, and because the hydrogen bond in the Xylitol fragrant polyurethane molecular is evenly distributed the electric charge in the molecule relatively, make intermolecular orientation force that the trend of reducing be arranged, further limited polymer crystallization, make that Xylitol fragrant urethane is amorphous polymer, this result with the X-ray diffraction analysis gained is consistent.
Accompanying drawing 4 is Xylitol fragrant urethane TG curve.By the thermal weight loss collection of illustrative plates as can be known, sample comparatively significantly weightlessness be divided into three phases, the fs: the weightlessness that occurred before 200 ℃ is because in the sample due to the sloughing of residual small-molecule substances such as solvent; Subordinate phase,
The weightlessness of 200 ℃～260 ℃ of appearance is because the weightlessness that the fracture of the carbamate groups in the sample causes.The mechanism of molecular breakdown is as shown below:
Phase III: 260 ℃～400 ℃, because the weightlessness that the decomposition of soft or hard section produces in the sample, wherein, 260 ℃～320 ℃ is the decomposition of hard section, and 320 ℃～400 ℃ is soft section decomposition.Because the heat decomposition temperature of polymkeric substance depends on the thermotolerance of various groups in the macromolecular structure, and rigidity benzene ring structure and large percentage in the Xylitol fragrant urethane are conducive to improve heat decomposition temperature, therefore, by DSC, TGA as seen, polymkeric substance has good thermostability.
Embodiment 3A kind of Xylitol fragrant urethane, a kind of Xylitol fragrant urethane, it is by soft section Xylitol and hard section Toluene-2,4-diisocyanate, the block polymer that the copolymerization of 4-vulcabond forms, its structural formula such as embodiment 1.
A kind of Xylitol fragrant polyurethane preparation method, step and condition are as follows:
Raw materials usedly see Table 3;
(1) pre-polymerization operation: earlier with ethyl acetate, join in the reactor, reaction system is vacuumized processing; under nitrogen protection, add Xylitol and 4; the 4-diphenylmethanediisocyanate stirs under room temperature and reaction 30min, then; in the reaction system that continues to stir, add the catalyzer dibutyl tin laurate; oil bath is warming up to 60 ℃, and reaction 4h detects in the solution-content of NCO with the Di-n-Butyl Amine method; when the content of-NCO reaches 5 ~ 10%, enter the chain extension operation.
(2) chain extension operation: in the system of step (1), add chainextender 1, the 2-propylene glycol, continue reaction 30min, ethyl acetate solvent is removed in decompression, obtain transparent viscous solution, by prolonging the stream method transparent viscous solution is poured in the mould, under the condition of room temperature, solidify 45h, the demoulding makes Xylitol fragrant urethane.
Performance to the polyurethane products of gained among the embodiment 1-3 detects.Preparation thickness is the sample of 0.55mm Xylitol fragrant urethane, is 86% ~ 88% with the transmittance of UV-7500 type measurement of ultraviolet-visible spectrophotometer sample.Show that this sample has light transmission preferably.Can be used as light transmissive material.
The sample of Xylitol fragrant urethane is positioned under the ultraviolet lamp shines, sample is 25cm apart from the distance of ultraviolet lamp, and ultraviolet lamp is 8 watts, shines after 7 days, and the transmittance of sample only descends 3%.The irradiation of show sample ultraviolet resistance.Can be used as anti-uv materials.
Measure the second-order transition temperature of the sample of Xylitol fragrant urethane with differential scanning calorimeter.Specifically see Table 4 content.
The result shows that its second-order transition temperature up to 171.6 ℃, has higher resistance toheat than common urethane.Can be Xylitol fragrant urethane as high temperature material.
The sample of Xylitol fragrant urethane acid (10% H
2SO
4), soaked 30 days in the alkali (10% NaOH solution), its light transmission and resistance toheat remain unchanged, namely the sample chemical resistance is strong, Xylitol fragrant urethane can be used as chemical resistant material.
Claims (1)
1. an Xylitol fragrant urethane is characterized in that, it is by soft section Xylitol and hard section Toluene-2,4-diisocyanate, the block polymer that the copolymerization of 4-vulcabond forms, and its structural formula is as follows:
Wherein,
Be soft section,
Be hard section.
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| CN2013102066390A CN103289054A (en) | 2013-05-30 | 2013-05-30 | Xylitol aromatic polyurethane |
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| CN2013102066390A CN103289054A (en) | 2013-05-30 | 2013-05-30 | Xylitol aromatic polyurethane |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892882A (en) * | 2014-03-03 | 2015-09-09 | 长春工业大学 | Transparent polyurethane material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5218073A (en) * | 1990-10-15 | 1993-06-08 | E. I. Du Pont De Nemours And Compaany | Polyhydroxy urethanes formed by reaction of reduced sugars and organic diisocyanates |
| CN1119195A (en) * | 1994-04-08 | 1996-03-27 | 三井东压化学株式会社 | Composition for urethane-base plastic lens, urethane-base plastic lens obtained from the composition and process for the production of the plastic lens |
| CN101885829A (en) * | 2010-07-12 | 2010-11-17 | 中科院广州化学有限公司 | Alcohol end capping nonionic polyurethane cross-linking agent and preparation method and application thereof |
-
2013
- 2013-05-30 CN CN2013102066390A patent/CN103289054A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5218073A (en) * | 1990-10-15 | 1993-06-08 | E. I. Du Pont De Nemours And Compaany | Polyhydroxy urethanes formed by reaction of reduced sugars and organic diisocyanates |
| CN1119195A (en) * | 1994-04-08 | 1996-03-27 | 三井东压化学株式会社 | Composition for urethane-base plastic lens, urethane-base plastic lens obtained from the composition and process for the production of the plastic lens |
| CN101885829A (en) * | 2010-07-12 | 2010-11-17 | 中科院广州化学有限公司 | Alcohol end capping nonionic polyurethane cross-linking agent and preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892882A (en) * | 2014-03-03 | 2015-09-09 | 长春工业大学 | Transparent polyurethane material and preparation method thereof |
| CN104892882B (en) * | 2014-03-03 | 2018-02-27 | 长春工业大学 | A kind of transparent polyurethane material and preparation method thereof |
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Application publication date: 20130911 |