CN104725832A - Hydroxylation rare earth/polyurethane hybrid material and preparation method thereof - Google Patents
Hydroxylation rare earth/polyurethane hybrid material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hydroxylation rare earth/polyurethane hybrid material and a preparation method thereof. The preparation method comprises the following steps: taking the hydroxylation rare earth obtained by using the hydrochloric acid and the hydrogen peroxide to process the rare earth oxide as a chain extender of the polyurethane elastomer, and performing reaction on the chain extender and a prepolymer to obtain the hydroxylation rare earth/polyurethane hybrid material. In the preparation process of the polyurethane, the dihydric alcohol or diamine chain extender cannot be added; due to the introduction of the hydroxylation rare earth, the rare earth/polyurethane hybrid network is constructed, the effect of a similar micromolecule chain extender is played and the effect of the network structure is strengthened through a coordinate bond on the surface. The hydroxylation rare earth provided by the method is simple in preparation method, uniformly dispersed in the polyurethane matrix, strong in interfacial adhesion with the polyurethane matrix and additionally has a reinforcing effect. The obtained material has the characteristics of excellent strength, elasticity, abrasion resistance, heat resistance, oil resistance and solvent resistance, and is simple in preparation process and low in cost.
Description
Technical field
The invention belongs to Materials science and technical field, be specifically related to a kind of hydroxylation rare earth/polyurethane hybridization material and preparation method thereof.
Background technology
Urethane is a kind of multifunctional material, there is excellent over-all properties, as the mechanical property of excellence, elasticity, wear resistance and low-temperature performance, good organic solvent resistance, performance variable range is wide, building-up properties is good, in many technical fields as having a wide range of applications in porous plastics, coating, elastomerics, binding agent, fiber and matrix material etc.
Rare earth ion has abundant electronic level, and ionic radius is comparatively large, and electric charge is higher, and has stronger coordination ability, therefore shows optical, electrical, the magnetic property of many excellences, is described as the treasure-house of novel material.Normal containing some polar groups in macromolecular compound, by rare earth ion and Electronic interactions, for polymer modification provides a kind of new approach, as luminescent material (absorption of fluorescence, laser, selective light, radiation protection), magneticsubstance, catalyzer etc. can be used as.
Hybrid material is the forth generation material after single component material, matrix material and function-graded material.Wherein organic/inorganic hybridization material is a kind of nano level heterogeneous material of even macroscopic, wherein have at least the size of a phase to have a dimension at least in nanometer scale, and nanophase is alternate with other chemical action (covalent linkage etc.) or physical action (hydrogen bond etc.) compound on nanometer level.Wherein, organic phase can be the macromolecular materials such as plastics, fiber, rubber and biomacromolecule; Inorganic phase can be metal, oxide compound, pottery, semi-conductor etc.Organic/inorganic hybridization material has the characteristic of macromolecular material and inorganic materials concurrently, on the basis of the good characteristic such as film-forming properties, the transparency, flexibility, easily processing keeping macromolecular material, introduce the performances such as inorganic materials is heat-resisting, resistance to oxidation, solvent resistant, scratch resistance, high strength, high rigidity simultaneously, sometimes go back the synergy in forming property, occur some new performances.The application of organic/inorganic hybridization material is comparatively extensive, can be used as structured material and the use of various functional materials.
Along with elastomerics Application Areas is towards the expansion of electronic applications, aerospace field, the performance such as mechanics, calorifics of Polyurethane Thermoplastic Elastomer is had higher requirement.Existing result of study shows, in Polyurethane Thermoplastic Elastomer, introduce inorganic particulate, can improve its mechanical strength and resistance toheat to a certain extent.But owing to not yet solving organic consistency with inorganic materials and interface cohesion problem, cause the performance of the actual inorganic modified Thermoplastic polyurethane elastomer material obtained not ideal enough.
At present, the research about polyurethane-base organic/inorganic hybridization material mainly contains: urethane/SiO
2hybrid material, urethane/polynite hybrid materials etc., the research of the rare-earth hybridized material of urethane/hydroxylation is then relatively less.Usual employing Rong Jiao ?gel method prepare urethane/SiO
2hybrid material, however these methods be all be all substantially do not change urethane composition namely must add the condition of chainextender (as small molecules diamine, dibasic alcohol) under add mineral filler.Owing to there is a large amount of hydrogen bond between polyurethane molecular chain, the existence of these hydrogen bonds makes urethane produce excellent mechanical property just, and the membership that adds of mineral filler produces buffer action to hydrogen bond, weaken intermolecular reactive force, thus cause the decline of material mechanical performance, therefore, polyurethane material seldom adds filler usually.
Therefore, need to research and develop a kind of weak point that can overcome above-mentioned technology, significantly improve mechanical property and the over-all properties of urethane, and the preparation method of the polyurethane hybridization material of practical, simple, energy-conservation, non-environmental-pollution.
Summary of the invention
The present invention is directed to Problems existing in the preparation method of above-mentioned polyurethane hybridization material, propose a kind of hydroxylation rare earth/polyurethane hybridization material and preparation method thereof.
The micro-nano hybrid material of indication of the present invention is on the basis of above-mentioned hybrid material concept, by the dimension enlargement of inorganic nano phase to from nanometer to micron order.The inorganic particulate that the present invention selects is the micron-sized hydroxylation rare earth of surface through hydroxylation process, these hydroxyls can react with the isocyanate groups of polyurethane prepolymer end, generate carbamate, thus produce covalent linkage connection, make urethane when without the need to adding chainextender, with form chemical bond closely between filler and be connected, final urethane and hydroxylation rare earth form space net structure jointly, obtain the micro-nano hybrid material (accompanying drawing 1) of excellent property.
Specifically, the present invention adopts polyurethane prepolymer fully to mix with surface modified hydroxylation rare earth, by rare earth Biao Mian ?OH directly with base polyurethane prepolymer for use as end of the chain ?NCO react at a certain temperature, generation hydroxylation rare earth/polyurethane hybridization material.Wherein a small amount of hydroxylation rare earth plays obvious reinforcement hybrid material mechanical property in hybrid material, the exotic materials of thermal characteristics.
The technical scheme of this invention:
A kind of preparation method of hydroxylation rare earth/polyurethane hybridization material, using the hydroxylation rare earth of hydrochloric acid and hydrogen peroxide treatment rare earth oxide gained as the chainextender of polyurethane elastomer, again chainextender and performed polymer are reacted, obtain hydroxylation rare earth/polyurethane hybridization material; Described performed polymer is generated by polyvalent alcohol and isocyanate reaction; Described polyvalent alcohol is polyether Glycols or polyester diol; Described isocyanic ester is vulcabond or polyisocyanates; Wherein do not add other organic molecule chainextenders.The wherein mol ratio nNCO/nOH=1.5 ~ 5.0:1 of isocyanate group and hydroxyl, adds the hydroxylation rare earth accounting for polyurethane prepolymer weight 0.1% ~ 5%, mixes the mixture obtaining polyurethane prepolymer and hydroxyl rare earth.Calculate by weight, the content of polyether Glycols or polyester diol, isocyanic ester, hydroxylation rare earth is as follows:
The preparation of hydroxylation rare earth, calculates by weight, and the content of rare earth oxide, hydrochloric acid, deionized water and hydrogen peroxide is as follows:
Aforesaid method, comprises the following steps:
(1) polyvalent alcohol vacuum-drying at temperature 80 ~ 100 DEG C is fully dewatered, isocyanic ester is added by the mol ratio nNCO/nOH=1.5:1 ~ 5.0:1 of isocyanate group and hydroxyl, in 50 ~ 90 DEG C of reactions 30 minutes to 5 hours, obtain end group Wei ?the base polyurethane prepolymer for use as of NCO;
(2) rare earth oxide 5 ~ 50g is dissolved in 5 ~ 50g deionized water, wherein adds 5 ~ 10g hydrochloric acid, first by rare earth oxide chlorination; Add 5 ~ 10g hydrogen peroxide again, continuous stirring reaction is after 10 ~ 30 minutes, with 2000 ~ 4000 revs/min of centrifugation 30 minutes in supercentrifuge, remove supernatant liquid, lower sediment is dried in 80 ~ 120 DEG C of vacuum drying ovens, grinds for subsequent use, hydroxylation rare earth can be obtained; Its chemical reaction is as follows:
R
xO
y+HCl→RCl
m
RCl
m+H
2O
2→R(OH)
m
Wherein, x is 1 ~ 11; Y is 1 ~ 20; M>1;
(3) end group that step (1) obtains Wei ?NCO base polyurethane prepolymer for use as in add the hydroxylation rare earth that step (2) obtains, mix the mixture obtaining polyurethane prepolymer and hydroxyl rare earth; Add the catalyzer accounting for isocyanate 0.01% ~ 2.0% more wherein, obtain mixture; Hydroxylation rare earth adding quantity meets: hydroxylation rare earth accounts for polyurethane prepolymer and hydroxyl lucium total mass 0.1% ~ 5%;
(4) mixture that obtains of step (3) was 20 ~ 130 DEG C of curing moldings 30 minutes to 7 days, obtained hydroxylation rare earth/polyurethane hybridization material.
In aforesaid method, described polyether Glycols be PTMG, polyoxytetramethylene glycol, polycyclic propylene oxide glycol or Si hydrogen Fu Nan ?propylene oxide copolyethers; Described polyether Glycols molecular weight is 1000 ~ 3000g/mol; Described polyester diol is polycarbonate diol, polycaprolactone glycol or hexanodioic acid system polyester; Described polyester diol molecular weight is 1000 ~ 3000g/mol.
In aforesaid method, described isocyanic ester is containing more than one in the aromatic isocyanate of two or more isocyanate groups, aliphatic isocyanates, alicyclic isocyanate.
In aforesaid method, described rare earth oxide comprises the oxide compound of lanthanon, scandium or yttrium element; Described lanthanon comprises lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium.
In aforesaid method, in step (3), add catalyzer, added catalyzer accounts for 0.01% ~ 2.0% of isocyanate, and the kind of described catalyzer is one or more mixtures in organotin catalysts or tertiary amine catalyst.
In aforesaid method, also comprise step (5), namely the polyurethane hybridization material of hydroxyl rare earth for preparing of step (4) 20 ?130 DEG C of after fixing 30 minutes to 7 days.
Compared with prior art, the present invention has the following advantages:
(1) the present invention need not use the chainextender such as dibasic alcohol, diamine to carry out chain extension to polyurethane molecular chain, the mineral filler of the surperficial hydroxyl adopted, there is the several functions such as chain extension, crosslinked, enhancing, urethane chain extension and crosslinking curing can not only be made within a short period of time, and after solidification, product has characteristic and the excellent dynamic properties such as excellent intensity, elasticity, heat-resisting, oil resistant, solvent resistant, even exceedes the conventional polyurethanes with the chainextender such as dibasic alcohol, diamine chain extension.
(2) the present invention adopts reaction in－situ composite algorithm to prepare the method for the polyurethane hybridization material of hydroxyl filler, and technique is simple, and reaction conditions is gentle, and cost is low, and generative process is polluted without chainextender, is conducive to environmental protection.
(3) the present invention first by chlorination and hydroxide by the modification of rare earth oxide hydroxylation, make the group major part Zhuan Bian Cheng on rare earth surface into ?OH, with base polyurethane prepolymer for use as Lian Duan ?NCO react fast.
(4) in the present invention modified RE Biao Mian ?OH and base polyurethane prepolymer for use as end of the chain ?NCO react cause You Ji ?inorganic hybridization, compared with the matrix material prepared with physical blending process, inorganic particulate is uniformly dispersed, and not easily reunites, and between inorganic particulate and polyurethane matrix, interface cohesion is strong.
(5) the present invention adds a small amount of hydroxylation rare earth another act as the strengthening agent of polyurethane system, after the cost composite factor considering rare earth, adds the over-all properties that a small amount of hydroxylation rare earth can significantly improve hybrid material.
Product of the present invention can be used for polyurethane elastomer product, can be used for again urethane foam, coating, tamanori, plastic toughening, water-proof material etc.
Accompanying drawing explanation
Fig. 1 is the formation structural representation of hydroxylation rare earth/polyurethane hybridization material.
Embodiment
Do specifically to describe in detail further to the present invention below in conjunction with specific embodiment, but embodiments of the present invention are not limited thereto, for the processing parameter do not indicated especially, can refer to routine techniques and carry out.
Embodiment 1:
A kind of hydroxylation rare earth/polyurethane hybridization material and preparation method thereof, its step as shown in Figure 1.
(1) 10g lanthanum sesquioxide (La is taken
2o
3) be positioned in beaker, add 10g deionized water dissolving, stir, add 5g hydrochloric acid (HCl) and constantly stir 5 minutes afterwards, then add 5g hydrogen peroxide (H
2o
2) continue stirring 10 minutes, mixed solution to be poured in centrifuge tube with 2000 revs/min after centrifugal 30 minutes, take off after at layer is deposited in 100 DEG C vacuum-drying fully dewaters, grind for subsequent use.
(2) by 71g molecular weight be the polyoxypropyleneglycol (PPG) of 2000 after vacuum-drying is fully dewatered at 110 DEG C, be cooled to 80 DEG C and add 19g tolylene diisocyanate (TDI), react 2 hours, obtained base polyurethane prepolymer for use as.
(3) add 0.1g step (1) in obtained in step (2) base polyurethane prepolymer for use as, rapid stirring, mixes.
(4) step (3) is placed in 120 DEG C of mould curing moldings 1 hour, after taking out from mould, is placed in baking oven 110 DEG C of after fixing again 4 hours, place the rear test performance of cooling.
Embodiment 2:
(1) 5g lanthanum sesquioxide (La is taken
2o
3) be positioned in beaker, add 10g deionized water dissolving, stir, add 10g hydrochloric acid (HCl) and constantly stir 10 minutes afterwards, then add 10g hydrogen peroxide (H
2o
2) continue stirring 15 minutes, mixed solution to be poured in centrifuge tube with 4000 revs/min after centrifugal 50 minutes, take off after at layer is deposited in 110 DEG C vacuum-drying fully dewaters, grind for subsequent use.
(2) be that the polytetrahydrofuran diol (PTMEG) of 1000 is after at 130 DEG C, vacuum-drying is fully dewatered by 56g molecular weight, be cooled to 70 DEG C and add 24g tolylene diisocyanate (TDI), react 1 hour, obtained base polyurethane prepolymer for use as.
(3) add 0.5g step (1) successively in obtained in step (2) base polyurethane prepolymer for use as, rapid stirring, mixes.
(4) step (3) is placed in 110 DEG C of mould curing moldings 2 hours, after taking out from mould, is placed in baking oven 100 DEG C of after fixing again 8 hours, place the rear test performance of cooling.
Embodiment 3:
(1) 5g samarium sesquioxide (Sm is taken
2o
3) be positioned in beaker, add 8g deionized water dissolving, stir, add 5g hydrochloric acid (HCl) and constantly stir 20 minutes afterwards, then add 5g hydrogen peroxide (H
2o
2) continue stirring 20 minutes, mixed solution to be poured in centrifuge tube with 3000 revs/min after centrifugal 60 minutes, take off after at layer is deposited in 100 DEG C vacuum-drying fully dewaters, grind for subsequent use.
(2) be that the polycaprolactone glycol (PCL) of 1000 is after at 120 DEG C, vacuum-drying is fully dewatered by 61g molecular weight, be cooled to 80 DEG C and add 22g hexamethylene diisocyanate (HDI), and to drip quality be that the dibutyl tin laurate of 0.1% of HDI quality reacts 2.5 hours, obtained base polyurethane prepolymer for use as.
(3) add 2g step (1) successively in obtained in step (2) base polyurethane prepolymer for use as, rapid stirring, mixes.
(4) step (3) is placed in 110 DEG C of mould curing moldings 2 hours, after taking out from mould, is placed in baking oven 100 DEG C of after fixing again 7 days, place the rear test performance of cooling.
Embodiment 4:
(1) 5g yttrium oxide (Y is taken
2o
3) be positioned in beaker, add 7g deionized water dissolving, stir, add 8g hydrochloric acid (HCl) and constantly stir 5 minutes afterwards, then add 10g hydrogen peroxide (H
2o
2) continue stirring 10 minutes, mixed solution to be poured in centrifuge tube with 4000 revs/min after centrifugal 30 minutes, take off after at layer is deposited in 110 DEG C vacuum-drying fully dewaters, grind for subsequent use.
(2) be that the polypropylene adipate (PPA) glycol (PPA) of 1000 is after at 110 DEG C, vacuum-drying is fully dewatered by 49g molecular weight, be cooled to 90 DEG C and add 16g isophorone diisocyanate (IPDI), and to drip quality be that the stannous octoate of 0.1% of IPDI quality reacts 3 hours, obtained base polyurethane prepolymer for use as.
(3) add 5g step (1) successively in obtained in step (2) base polyurethane prepolymer for use as, rapid stirring, mixes.
(4) step (3) is placed in 120 DEG C of mould curing moldings 1 hour, after taking out from mould, is placed in baking oven 100 DEG C of after fixing again 24 hours, place the rear test performance of cooling.
Embodiment 5:
(1) taking 6g mishmetal is positioned in beaker, adds 5g deionized water dissolving, stirs, and adds 15g hydrochloric acid (HCl) and constantly stirs 10 minutes afterwards, then add 20g hydrogen peroxide (H
2o
2) continue stirring 10 minutes, mixed solution to be poured in centrifuge tube with 4000 revs/min after centrifugal 30 minutes, take off after at layer is deposited in 110 DEG C vacuum-drying fully dewaters, grind for subsequent use.
(2) be that the poly-adipate glycol propylene glycol ester glycol (PEPA) of 3000 is after at 90 DEG C, vacuum-drying is fully dewatered by 55g molecular weight, be cooled to 80 DEG C and add 18g 4,4 ’ ?diphenylmethanediisocyanate (MDI) react 2 hours, obtained base polyurethane prepolymer for use as.
(3) add 2g step (1) successively in obtained in step (2) base polyurethane prepolymer for use as, rapid stirring, mixes.
(4) step (3) is placed in 130 DEG C of mould curing moldings 1 hour, after taking out from mould, is placed in baking oven 110 DEG C of after fixing again 48 hours, place the rear test performance of cooling.
Embodiment 6:
The preparation of pure PU urethane, specifically comprises the following steps:
(1) be that the polytetrahydrofuran diol (PTMEG) of 1000 is after at 130 DEG C, vacuum-drying is fully dewatered by 65g molecular weight, be cooled to 80 DEG C and add 30g tolylene diisocyanate (TDI), react 1.5 hours, obtained base polyurethane prepolymer for use as.
(2) add 3g butyleneglycol (BD) in obtained in step (1) base polyurethane prepolymer for use as, and drip the dibutyl tin laurate that quality is TDI quality 0.1%, stir after mixing.
(3) step (2) is placed in 120 DEG C of mould curing moldings 2 hours, after taking out from mould, is placed in baking oven 100 DEG C of after fixing again 48 hours, place the rear test performance of cooling.
Table 1 is the data of mechanical of hydroxylation rare earth/polyurethane hybridization material and the pure PU obtained in above-mentioned example.Wherein the tensile strength of hydroxylation rare earth/polyurethane hybridization material, the index such as tear strength and stress at definite elongation are significantly improved than pure PU.
Table 1
Table 2 is the thermal performance test data of the hydroxylation rare earth/polyurethane hybridization material obtained in above-mentioned example.Can find out, the thermostability of pure PU is poor, and after adding hydroxylation rare earth, the thermostability of hybrid material significantly improves.
Table 2
In sum, hydroxylation rare earth/polyurethane hybridization material of the present invention and preparation method thereof, modified owing to utilizing rare earth oxide to carry out hydroxylation, there is high reaction activity.A small amount of adds in polyurethane system the mechanical property and thermotolerance that substantially increase hybrid material to.When the introduction volume of hydroxylation rare earth is 0.1 ~ 5wt%, the tensile strength of gained hydroxylation rare earth/polyurethane hybridization material is 29.6 ~ 41.5MPa, and elongation at break is 423 ~ 478%, and tear strength is 62 ~ 70MPa, shore hardness is 80 ~ 82 degree, and maximum decomposition temperature is 420 ~ 442 DEG C.
The above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.All any amendments done within the spirit and principles in the present invention, equivalent to replace and improvement etc., within the protection domain that all should be included in the claims in the present invention.
Claims (8)
1. the preparation method of hydroxylation rare earth/polyurethane hybridization material, it is characterized in that, using the hydroxylation rare earth of hydrochloric acid and hydrogen peroxide treatment rare earth oxide gained as the chainextender of polyurethane elastomer, again chainextender and performed polymer are reacted, obtain hydroxylation rare earth/polyurethane hybridization material; Described performed polymer is generated by polyvalent alcohol and isocyanate reaction; Described polyvalent alcohol is polyether Glycols or polyester diol; Described isocyanic ester is vulcabond or polyisocyanates.
2. preparation method according to claim 1, is characterized in that, comprises the following steps:
(1) polyvalent alcohol vacuum-drying at temperature 80 ~ 100 DEG C is fully dewatered, isocyanic ester is added by the mol ratio nNCO/nOH=1.5:1 ~ 5.0:1 of isocyanate group and hydroxyl, in 50 ~ 90 DEG C of reactions 30 minutes to 5 hours, obtain the base polyurethane prepolymer for use as that end group is-NCO;
(2) rare earth oxide 5 ~ 50g is dissolved in 5 ~ 50g deionized water, wherein adds 5 ~ 10g hydrochloric acid, first by rare earth oxide chlorination; Add 5 ~ 10g hydrogen peroxide again, continuous stirring reaction is after 10 ~ 30 minutes, with 2000 ~ 4000 revs/min of centrifugation 30 minutes in supercentrifuge, remove supernatant liquid, lower sediment is dried in 80 ~ 120 DEG C of vacuum drying ovens, grinds for subsequent use, hydroxylation rare earth can be obtained; Its chemical reaction is as follows:
Wherein, x is 1 ~ 11; Y is 1 ~ 20; M>1;
(3) end group that step (1) obtains is add the hydroxylation rare earth that step (2) obtains in the base polyurethane prepolymer for use as of-NCO, mixes the mixture obtaining polyurethane prepolymer and hydroxyl rare earth; Add the catalyzer accounting for isocyanate 0.01% ~ 2.0% more wherein, obtain mixture; Hydroxylation rare earth adding quantity meets: hydroxylation rare earth accounts for polyurethane prepolymer and hydroxyl lucium total mass 0.1% ~ 5%;
(4) mixture that obtains of step (3) was 20 ~ 130 DEG C of curing moldings 30 minutes to 7 days, obtained hydroxylation rare earth/polyurethane hybridization material.
3. preparation method according to claim 2, is characterized in that, described polyether Glycols is PTMG, polyoxytetramethylene glycol, polycyclic propylene oxide glycol or THF-PO copolymer; Described polyether Glycols molecular weight is 1000 ~ 3000g/mol; Described polyester diol is polycarbonate diol, polycaprolactone glycol or hexanodioic acid system polyester; Described polyester diol molecular weight is 1000 ~ 3000g/mol.
4. preparation method according to claim 2, is characterized in that, described isocyanic ester is containing more than one in the aromatic isocyanate of two or more isocyanate groups, aliphatic isocyanates, alicyclic isocyanate.
5. preparation method according to claim 2, is characterized in that, described rare earth oxide comprises the oxide compound of lanthanon, scandium or yttrium element; Described lanthanon comprises lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium.
6. preparation method according to claim 2, it is characterized in that, add catalyzer in step (3), added catalyzer accounts for 0.01% ~ 2.0% of isocyanate, and the kind of described catalyzer is more than one mixtures in organotin catalysts or tertiary amine catalyst.
7. according to the preparation method described in claim 2, it is characterized in that, also comprise step (5), namely the polyurethane hybridization material of hydroxyl rare earth for preparing of step (4) was 20-130 DEG C of after fixing 30 minutes to 7 days.
8. prepare a kind of hydroxylation rare earth/polyurethane hybridization material by the preparation method described in any one of claim 1-7.
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| CN112708256A (en) * | 2020-12-27 | 2021-04-27 | 宁波长阳科技股份有限公司 | Ultraviolet light aging resistant fluorescent TPU (thermoplastic polyurethane) film material as well as preparation method and application thereof |
| CN113214637A (en) * | 2021-05-17 | 2021-08-06 | 福建师范大学泉港石化研究院 | Polyurethane with uvioresistant performance and preparation method thereof |
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