CN112079749A - Diphenylethane diisocyanate/pentaerythritol prepolymer and preparation method and application thereof - Google Patents
Diphenylethane diisocyanate/pentaerythritol prepolymer and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
- C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
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- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7843—Nitrogen containing -N-C=0 groups containing urethane groups
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Abstract
The invention provides a diphenylethane diisocyanate/pentaerythritol prepolymer and a preparation method and application thereof. The prepolymer has a structure shown in formula (I):
wherein, said R1And R2Each independently selected from H or alkyl. The storage period of the diphenylethane diisocyanate/pentaerythritol prepolymer prepared by the invention can reach 60 days, and the stability is 240 times that of DEDI. Compared with the elastomer prepared from MDI and TDI, the elastomer prepared from the diphenyl ethane diisocyanate/pentaerythritol prepolymer has greatly improved properties such as tensile strength, tearing strength and the like.
Description
Technical Field
The invention relates to the field of material chemistry, in particular to a diphenylethane diisocyanate/pentaerythritol prepolymer and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Polyurethane (PU) is a polymer containing a plurality of carbamate groups (-NHCOO-) on the main chain of a high molecular structure, and the polyurethane material is a synthetic material with wide application and is mainly prepared by reacting polybasic organic isocyanate and various hydrogen donor compounds (such as compounds containing terminal hydroxyl groups generally). Because the isocyanate and the polyol compound have different types of functional groups and different numbers of functional groups, polyurethane products with excellent performance and various expression forms can be prepared by different synthesis processes and materials. The products widely applied in the market comprise very soft or hard plastic foam, elastomer rubber with excellent wear resistance, paint and coating with high gloss, adhesive with excellent bonding performance and the like.
The united states is an important major consumer nation of PU, which is mainly used to make elastomers, and is widely used, for example, in automobile bumpers, dashboards, and the like, due to its excellent toughness, elastic strength, abrasion resistance, shock resistance, and chemical resistance. China is the largest consumer of PU and is mainly used for soft foam, hard foam, elastomers, adhesives, coatings, auxiliaries and the like.
The most used isocyanates in the polyurethane industry today are mainly Toluene Diisocyanate (TDI) and diphenylmethane diisocyanate (MDI), and secondly Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), Xylylene Diisocyanate (XDI), dicyclohexylmethylene diisocyanate (H12MDI) and the like. The existing PU monomer raw materials have poor stability, and the prepared PU product also has some defects, such as poor heat resistance, lower softening temperature and decomposition temperature, and the like, thereby limiting the application of the PU monomer in certain fields.
Diphenylethane diisocyanate (DEDI, see CN110903216A) is a novel monomer raw material for preparing PU, but the DEDI monomer has poor stability and short storage time, and is not beneficial to practical application.
Disclosure of Invention
Aiming at the problems of poor isocyanate stability and short storage time in the prior art, the invention provides a prepolymer (DEDI/PE prepolymer) of diphenylethane diisocyanate (DEDI) and pentaerythritol (PE for short), wherein the storage time of the prepolymer can reach 60 days, and the stability of the prepolymer is 240 times that of a DEDI monomer. Meanwhile, the DEDI/PE prepolymer has no symmetry, so that a product with good flexibility and high transparency can be obtained, the mechanical property of a polyurethane product is improved, and the use requirement of a synthetic polyurethane material can be well met.
Specifically, the invention is realized by the following technical scheme:
in a first aspect of the invention, the invention provides a DEDI/PE prepolymer, which is characterized in that the DEDI/PE prepolymer has a structure shown in formula (I),
wherein, R is1And R2Each independently selected from H and alkyl.
The substitutable sites of two benzene rings on the same diphenylethane group are respectively marked as C-1, C-2, C-3, C-4, C-5 and C-6 sites, as well as C-1', C-2', C-3', C-4', C-5 'and C-6' sites, and can be specifically shown as formula (I).
The four diphenylethane groups in the formula (I) are in a symmetrical state, and the substitution types and the positions of the four diphenylethane groups are the same. The positions of the substituent groups of the outer benzene rings are C-1, C-2, C-3, C-4, C-5 and C-6, the positions of the substituent groups of the inner benzene rings are C-1', C-2', C-3', C-4', C-5 'and C-6', the positions of C-1, C-2, C-3, C-4, C-5 and C-6, and the positions of C-1', C-2', C-3', C-4', C-5 'and C-6' represent the relative positions of the substituent sites on different benzene rings, and are not limited absolutely.
In some embodiments of the invention, when R1And R2When the substituents are the same, the compound is a cyclic compound,
the R is1At the C-2 or C-3 position of the diphenylethane group, the R2At the C-2 'or C-3' position of the diphenylethane group;
preferably, the alkyl group is C1-C6Straight or branched alkyl, preferably C1-C3Straight or branched chain alkyl.
Preferably, the alkyl group is selected from methyl, ethyl and n-propyl.
Preferably, the-NH-is located at the C-4, C-5 or C-6 position of the diphenylethane group and the-NCO is located at the C-4', C-5' or C-6' position of the diphenylethane group.
Preferably, R1At C-2 or C-3 position of the diphenylethane group and R1Is H or methyl or ethyl or n-propyl; r2At C-2 'or C-3' position of the diphenylethane group and R2Is H or methyl or ethyl or n-propyl; -NH-is in the C-4 or C-5 position of the diphenylethylene group; -NCO is located at the C-4 'or C-5' position of the diphenylethylene glycol group.
Further preferably, the DEDI/PE prepolymer is selected from the following structures:
diphenylethane-4, 4' -diisocyanate/pentaerythritol prepolymer;
2,2 '-dimethyl-diphenylethane-4, 4' -diisocyanate/pentaerythritol prepolymer;
2,2 '-dimethyl-diphenylethane-5, 5' -diisocyanate/pentaerythritol prepolymer;
2,2 '-dimethyl-diphenylethane-6, 6' -diisocyanate/pentaerythritol prepolymer;
2,2 '-diethyl-diphenylethane-4, 4' -diisocyanate/pentaerythritol prepolymer;
2,2 '-di-n-propyl-diphenylethane-4, 4' -diisocyanate/pentaerythritol prepolymer;
3,3 '-dimethyl-diphenylethane-6, 6' -diisocyanate/pentaerythritol prepolymer.
In some embodiments of the invention, when R1And R2When the substituent group is different from the substituent group,
the R is1At the C-2 or C-3 position of the diphenylethane group, the R2At the C-2 'or C-3' position of the diphenylethane group;
preferably, the alkyl group is C1-C6Straight or branched chain alkyl.
Preferably, the alkyl group is C1-C3Straight or branched chain alkyl.
Preferably, the alkyl group is selected from methyl, ethyl and n-propyl.
Preferably, the-NH-is located at the C-4, C-5 or C-6 position of the diphenylethane group and the-NCO is located at the C-4', C-5' or C-6' position of the diphenylethane group.
In a second aspect of the present invention, the present invention provides a method for preparing a DEDI/PE prepolymer, which comprises reacting diphenylethane diisocyanate and pentaerythritol as raw materials.
Preferably, the preparation method comprises: dissolving diphenylethane diisocyanate in a solvent A, heating, adding pentaerythritol, stirring, heating and carrying out heat preservation reaction to obtain a reactant; and after the reaction is judged to be finished, adding the solvent A, stirring, cooling and discharging to obtain liquid, namely the diphenyl ethane diisocyanate/pentaerythritol prepolymer.
In some embodiments of the invention, the diphenylethane diisocyanate is selected from the group consisting of diphenylethane-6, 6 '-diisocyanate, diphenylethane-5, 5' -diisocyanate, diphenylethane-4, 4 '-diisocyanate, 2' -dimethyldiphenylethane-6, 6 '-diisocyanate, 2' -dimethyldiphenylethane-5, 5 '-diisocyanate, 2' -dimethyldiphenylethane-4, 4 '-diisocyanate, 2' -dimethyldiphenylethane-4, 5 '-diisocyanate, 2' -dimethyldiphenylethane-4, 6 '-diisocyanate, 2' -dimethyldiphenylethane-5, 6' -diisocyanate, 2' -diethyldiphenylethane-6, 6' -diisocyanate, 2' -ethylmethyldiphenylethane-5, 5' -diisocyanate, 2' -diethyldiphenylethane-4, 4' -diisocyanate, 2' -diethyldiphenylethane-4, 5' -diisocyanate, 2' -diethyldiphenylethane-4, 6' -diisocyanate, 2' -diethyldiphenylethane-5, 6' -diisocyanate, 2' -di-n-propyldiphenylethane-6, 6' -diisocyanate, 2' -di-n-propyldiphenylethane-5, 5' -diisocyanate, 2,2' -di-n-propyldiphenylethane-4, 4' -diisocyanate, 2' -di-n-propyldiphenylethane-4, 5' -diisocyanate, 2' -di-n-propyldiphenylethane-4, 6' -diisocyanate, 2' -di-n-propyldiphenylethane-5, 6' -diisocyanate, 3' -dimethyldiphenylethane-6, 6' -diisocyanate, 3' -dimethyldiphenylethane-5, 5' -diisocyanate, 3' -dimethyldiphenylethane-4, 4' -diisocyanate, 3' -diethyldiphenylethane-6, 6' -diisocyanate, 3' -diethyldiphenylethane-5, 5' -diisocyanate, 3' -diethyldiphenylethane-4, 4' -diisocyanate, 3' -di-n-propyldiphenylethane-6, 6' -diisocyanate, 3' -di-n-propyldiphenylethane-5, 5' -diisocyanate, and 3,3' -di-n-propyldiphenylethane-4, 4' -diisocyanate;
further the DEDI is selected from the group consisting of diphenylethane-6, 6' -diisocyanate, diphenylethane-5, 5' -diisocyanate, diphenylethane-4, 4' -diisocyanate, 2' -dimethyldiphenylethane-6, 6' -diisocyanate, 2' -dimethyldiphenylethane-5, 5' -diisocyanate, 2' -dimethyldiphenylethane-4, 4' -diisocyanate, 3' -dimethyldiphenylethane-5, 5' -diisocyanate, 3' -dimethyldiphenylethane-4, 4' -diisocyanate, 3' -diethyldiphenylethane-5, 5' -diisocyanate, 3,3 '-diethyldiphenylethane-4, 4' -diisocyanate.
In some embodiments of the invention, the solvent a is selected from inert solvents in which the aromatic hydrocarbon is not active;
preferably, the solvent a is selected from one or more of normal alkane, cyclohexane, benzene, toluene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, trichlorobenzene, sym-trichlorobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-xylene, m-xylene, p-xylene, hemimellitene, mesitylene, propylbenzene, ethyl acetate, n-propyl acetate, n-butyl acetate and benzyl acetate.
Preferably, the solvent a is an anhydrous solvent.
Water contained in raw materials, solvents and the like reacts with isocyanate to influence synthesis and stability of the prepolymer, so that the solvents need to be strictly dehydrated and need to react under strictly anhydrous conditions.
Preferably, the solvent A is used in an amount of 0.05L to 50L, preferably 0.5L to 2L, of diphenylethane diisocyanate per kg of solvent.
Preferably, the pentaerythritol is dissolved in advance with solvent a into a solution.
In some embodiments of the invention, the molar ratio of diphenylethane diisocyanate to pentaerythritol is from 1.0 to 10.0: 1.0, preferably from 2.5 to 5.0: 1.0.
In some embodiments of the invention, the reaction is carried out under nitrogen.
In some embodiments of the invention, the heating temperature is from 0.0 ℃ to 200 ℃, preferably from 50 ℃ to 100 ℃, and more preferably from 60 ℃ to 80 ℃.
Preferably, the heating and heat-preserving reaction temperature is 0.0-200 ℃, and preferably 60-120 ℃.
Preferably, the reaction time of the heating and heat preservation is 0.5-2h, and further 1 h.
Preferably, the two times of stirring are uniform stirring.
Preferably, the uniform stirring time is 15-45min, and further 30 min.
In some embodiments of the invention, the method for determining the end of the reaction is: sampling and analyzing the quantity fraction of the isocyanate matrix after the reaction is carried out for a certain time at the temperature preservation, detecting once every half an hour, and judging that the isocyanate matrix reaches the reaction end point when the difference value of the detection results of two consecutive times is within 0.1;
preferably, the mass fraction of the isocyanate groups is 1.0% -50.0%, preferably 5.0% -30.0%;
in some embodiments of the invention, the temperature reduction is to 30-50 ℃, further to 40 ℃.
In a third aspect of the invention, the invention provides a polyurethane material prepared from the DEDI/PE prepolymer.
In a fourth aspect of the invention, the invention provides the application of the DEDI/PE prepolymer or the preparation method thereof in a chemically synthesized material polyurethane.
The invention has the beneficial effects that:
the DEDI/PE prepolymer of the invention has a storage time of 60 days, and the stability is 240 times of that of a DEDI monomer, and the DEDI/PE prepolymer is beneficial to the practical application of preparing PU materials. The DEDI/PE prepolymer has no symmetry, is beneficial to obtaining a product with good flexibility and high transparency, improves the mechanical property of a polyurethane product, and can well meet the use requirement of synthesizing a polyurethane material.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only.
Diphenylethane diisocyanate (DEDI) can be prepared by those skilled in the art according to the method described in Chinese patent CN110903216A, and is incorporated herein in its entirety by Chinese patent CN 110903216A.
Example 1
Adding 100.00L of ethyl acetate into a reaction kettle, blowing nitrogen to remove moisture, adding 105.75kg of diphenylethane-4, 4' -diisocyanate, introducing nitrogen for protection, heating to 60 ℃, adding 13.62kg of pentaerythritol (12.00L of dehydrated ethyl acetate is used for dissolving into a solution in advance), stirring at a constant speed, carrying out heat preservation reaction at 60 ℃ for 1h, then sampling and analyzing the mass fraction (-NCO%) of isocyanate groups (according to GB/T13941-92 by a di-n-butylamine-hydrochloric acid titration method), wherein the NCO% is reduced along with the progress of the reaction, so as to determine the reaction degree, detecting once every half an hour, and determining that the reaction end point is reached when the difference value of the detection results of two consecutive times is within the range of 0.1. And after the reaction is finished, adding 10.00L of dehydrated ethyl acetate solvent, continuously stirring at a constant speed, cooling to 40 ℃, discharging, and obtaining colorless or light yellow transparent liquid, namely the DEDI/PE prepolymer.
The DEDI/PE prepolymer prepared in this example was chargedAnd (4) carrying out NMR analysis and detection,1H NMR(400MHz,CDCl3)2.71(m,8H,4×CH2),2.83(m,8H,4×CH2),4.24(m,8H,4×CH2),7.16(d,4H,4×CH),7.23(s,4H,4×CH),7.24(d,4H,4×CH),7.25(d,4H,4×CH),7.43(d,4H,4×CH),7.47(s,4H,4×CH),9.87(s,4H,4×NH)。
13C NMR(101MHz,CDCl3)36.44,36.44,36.44,36.44,36.47,36.47,36.47,36.47,58.95,58.95,58.95,58.95,70,67,118.56,118.56,118.56,118.56,121.12,121.12,121.12,121.12,122.03,122.03,122.03,122.03,124.50,124.50,124.50,124.50,126.51,126.51,126.51,126.51,129.97,129.97,129.97,129.97,130.03,130.03,130.03,130.03,130.72,130.72,130.72,130.72,132.81,132.81,132.81,132.81,133.05,133.05,133.05,133.05,134.47,134.47,134.47,134.47,135.75,135.75,135.75,135.75,136.67,136.67,136.67,136.67,152.23,152.23,152.23,152.23。
FT-IR (KBr pellet) measurement at 3250cm-1-3500cm-1(-NHCO cis NH stretching vibration), 2240cm-1-2280cm-1(-NCO characteristic absorption Peak), 1715cm-1-1750cm-1(amide I bond C ═ O), 1520cm-1-1560cm-1(amide II bond N-H deformation vibration) appears in 4 characteristic absorption peaks.
Through the analysis, the product is diphenyl ethane-4, 4' -diisocyanate/PE prepolymer.
The diphenylethane-4, 4' -diisocyanate/PE prepolymer showed a peak at 13.5min (20.5 min for DEDI monomer) and a content (normalized) of 90.0% as determined by Gel Permeation Chromatography (GPC).
Note: gel Permeation Chromatography (GPC) is a common test method for determining molecular weight and molecular weight distribution of high molecular polymers by using the time difference between substances having different relative molecular masses when they permeate a chromatographic column. Us Waters corporation GPC: model 1525 double pump, model 717 autosampler, and model 2487 refractive index detector. The testing conditions are that a Styrage HT2/3 type chromatographic column is adopted, and the column temperature is 40 ℃; the mobile phase was tetrahydrofuran, flow rate 1mL/min, PEG1510 (Gard's reagent) as standard. During detection, a sample is prepared into a tetrahydrofuran solution, the concentration is 0.5%, and the sample injection amount is 80 uL.
The following examples have the same GPC measurement conditions.
Example 2
Adding 100.00L of butyl acetate into a reaction kettle, blowing nitrogen to remove moisture, adding 116.95kg of 2,2 '-dimethyl-diphenylethane-4, 4' -diisocyanate, introducing nitrogen for protection, heating to 60 ℃, adding 13.60kg of pentaerythritol (12.00L of dehydrated butyl acetate is used for dissolving into solution in advance), stirring at a constant speed, carrying out heat preservation reaction at 60 ℃ for 1h, then sampling and analyzing the mass fraction (-NCO%) of isocyanate groups (according to GB/T13941-92 by a di-n-butylamine-hydrochloric acid titration method), wherein the NCO% is reduced along with the progress of the reaction, so as to determine the reaction degree, detecting once every half an hour, and judging that the reaction end point is reached when the difference of the detection results of two consecutive times is within the range of 0.1. And after the reaction is finished, adding 10.00L of dehydrated butyl acetate solvent, continuously stirring at a constant speed, cooling to 40 ℃, discharging, and obtaining colorless or light yellow transparent liquid, namely the DEDI/PE prepolymer.
NMR analysis and detection were carried out on the DEDI/PE prepolymer prepared in this example,1H NMR(400MHz,CDCl3)2.30(s,24H,8×CH3),2.71(m,8H,4×CH2),2.83(m,8H,4×CH2),4.24(m,8H,4×CH2),7.16(d,4H,4×CH),7.23(s,4H,4×CH),7.25(d,4H,4×CH),7.27(d,4H,4×CH),7.43(d,4H,4×CH),7.47(s,4H,4×CH),9.87(s,4H,4×NH)。
13C NMR(101MHz,CDCl3)19.13,19.13,19.13,19.13,19.16,19.16,19.16,19.16,36.44,36.44,36.44,36.44,36.47,36.47,36.47,36.47,58.95,58.95,58.95,58.95,70,67,118.57,118.57,118.57,118.57,121.13,121.13,121.13,121.13,122.04,122.04,122.04,122.04,124.51,124.51,124.51,124.51,126.52,126.52,126.52,126.52,129.98,129.98,129.98,129.98,130.04,130.04,130.04,130.04,130.73,130.73,130.73,130.73,132.82,132.82,132.82,132.82,133.06,133.06,133.06,133.06,134.48,134.48,134.48,134.48,135.76,135.76,135.76,135.76,136.68,136.68,136.68,136.68,152.24,152.24,152.24,152.24。
the product FT-IR (KBr pellet) was detected at 3250cm-1-3500cm-1(-NHCO cis NH stretching vibration), 2240cm-1-2280cm-1(-NCO characteristic absorption Peak), 1715cm-1-1750cm-1(amide I bond C ═ O), 1520cm-1-1560cm-1(amide II bond N-H deformation vibration) appears in 4 characteristic absorption peaks.
Through the above analysis, the product was a 2,2 '-dimethyl-diphenylethane-4, 4' -diisocyanate/PE prepolymer.
The product Gel Permeation Chromatography (GPC) detected that the peak of the 2,2 '-dimethyl-diphenylethane-4, 4' -diisocyanate/PE prepolymer is at 13.3min (the peak is at 20.5min of DEDI monomer), and the content (normalization method) is 92.0%.
Example 3
Adding 100.00L of benzyl acetate into a reaction kettle, blowing nitrogen to remove moisture, adding 122.75kg of 2,2 '-dimethyl-diphenylethane-5, 5' -diisocyanate, introducing nitrogen for protection, heating to 80 ℃, adding 13.60kg of pentaerythritol (12.00L of dehydrated benzyl acetate is used for dissolving into solution in advance), stirring at a constant speed, carrying out heat preservation reaction at 80 ℃ for 1h, then sampling and analyzing the mass fraction (-NCO%) of isocyanate groups (according to GB/T13941-92 by a di-n-butylamine-hydrochloric acid titration method), wherein the NCO% is reduced along with the progress of the reaction, so as to determine the reaction degree, detecting once every half an hour, and judging that the reaction end point is reached when the difference of the detection results of two consecutive times is within the range of 0.1. And after the reaction is finished, continuously stirring at a constant speed, cooling to 40 ℃, discharging, and obtaining colorless or light yellow transparent liquid, namely the DEDI/PE prepolymer.
NMR analysis and detection were carried out on the DEDI/PE prepolymer prepared in this example,1H NMR(400MHz,CDCl3)2.31(s,24H,8×CH3),2.72(m,8H,4×CH2),2.84(m,8H,4×CH2),4.25(m,8H,4×CH2),7.17(d,4H,4×CH),7.24(s,4H,4×CH),7.26(d,4H,4×CH),7.27(d,4H,4×CH),7.44(d,4H,4×CH),7.48(s,4H,4×CH),9.88(s,4H,4×NH)。
13C NMR(101MHz,CDCl3)19.14,19.14,19.14,19.14,19.17,19.17,19.17,19.17,36.45,36.45,36.45,36.45,36.48,36.48,36.48,36.48,58.96,58.96,58.96,58.96,70,69,118.58,118.58,118.58,118.58,121.14,121.14,121.14,121.14,122.05,122.05,122.05,122.05,124.52,124.52,124.52,124.52,126.53,126.53,126.53,126.53,129.99,129.99,129.99,129.99,130.05,130.05,130.05,130.05,130.74,130.74,130.74,130.74,132.83,132.83,132.83,132.83,133.07,133.07,133.07,133.07,134.49,134.49,134.49,134.49,135.77,135.77,135.77,135.77,136.69,136.69,136.69,136.69,152.25,152.25,152.25,152.25。
the product FT-IR (KBr pellet) was detected at 3250cm-1-3500cm-1(-NHCO cis NH stretching vibration), 2240cm-1-2280cm-1(-NCO characteristic absorption Peak), 1715cm-1-1750cm-1(amide I bond C ═ O), 1520cm-1-1560cm-1(amide II bond N-H deformation vibration) appears in 4 characteristic absorption peaks.
Through the above analysis, the product was a 2,2 '-dimethyl-diphenylethane-5, 5' -diisocyanate/PE prepolymer.
The product Gel Permeation Chromatography (GPC) detected that the peak of the 2,2 '-dimethyl-diphenylethane-5, 5' -diisocyanate/PE prepolymer is at 13.4min (the peak is at 20.5min of DEDI monomer), and the content (normalization method) is 93.0%.
Example 4
Adding 80.50L of chlorobenzene into a reaction kettle, blowing nitrogen to remove moisture, adding 120.00kg of 2,2 '-dimethyl-diphenylethane-6, 6' -diisocyanate, introducing nitrogen for protection, heating to 80 ℃, adding 13.60kg of pentaerythritol (15.00L of dehydrated chlorobenzene is used for dissolving into solution in advance), stirring at a constant speed, heating to 180 ℃, carrying out heat preservation reaction for 1h, sampling and analyzing the mass fraction (-NCO%) of isocyanate groups (according to GB/T13941-92 by a di-n-butylamine-hydrochloric acid titration method), wherein the NCO% is reduced along with the progress of the reaction, so as to determine the reaction degree, detecting once every half an hour, and judging that the reaction end point is reached when the difference of the detection results of two consecutive times is within the range of 0.1. And after the reaction is finished, continuously stirring at a constant speed, cooling to 40 ℃, discharging, and obtaining colorless or light yellow transparent liquid, namely the DEDI/PE prepolymer.
NMR analysis and detection were carried out on the DEDI/PE prepolymer prepared in this example,1H NMR(400MHz,CDCl3)2.32(s,24H,8×CH3),2.73(m,8H,4×CH2),2.85(m,8H,4×CH2),4.26(m,8H,4×CH2),7.19(d,4H,4×CH),7.22(m,4H,4×CH),7.25(d,4H,4×CH),7.29(d,4H,4×CH),7.45(d,4H,4×CH),7.49(s,4H,4×CH),9.89(s,4H,4×NH)。
13C NMR(101MHz,CDCl3)19.15,19.15,19.15,19.15,19.18,19.18,19.18,19.18,36.47,36.47,36.47,36.47,36.49,36.49,36.49,36.49,58.97,58.97,58.97,58.97,70,70,118.59,118.59,118.59,118.59,121.15,121.15,121.15,121.15,122.06,122.06,122.06,122.06,124.53,124.53,124.53,124.53,126.54,126.54,126.54,126.54,129.98,129.98,129.98,129.98,130.06,130.06,130.06,130.06,130.75,130.75,130.75,130.75,132.84,132.84,132.84,132.84,133.08,133.08,133.08,133.08,134.50,134.50,134.50,134.50,135.78,135.78,135.78,135.78,136.70,136.70,136.70,136.70,152.31,152.31,152.31,152.31。
the product FT-IR (KBr pellet) was detected at 3250cm-1-3500cm-1(-NHCO cis NH stretching vibration), 2240cm-1-2280cm-1(-NCO characteristic absorption Peak), 1715cm-1-1750cm-1(amide I bond C ═ O), 1520cm-1-1560cm-1(amide II bond N-H deformation vibration) appears in 4 characteristic absorption peaks.
Through the above analysis, the product was a 2,2 '-dimethyl-diphenylethane-6, 6' -diisocyanate/PE prepolymer.
The product Gel Permeation Chromatography (GPC) detected that the peak of the 2,2 '-dimethyl-diphenylethane-6, 6' -diisocyanate/PE prepolymer is at 13.1min (the peak is at 20.5min of DEDI monomer), and the content (normalization method) is 91.0%.
Example 5
Adding 90.00L of toluene into a reaction kettle, blowing nitrogen to remove water, adding 128.20kg of 2,2 '-diethyl-diphenylethane-4, 4' -diisocyanate, introducing nitrogen for protection, heating to 60 ℃, adding 13.60kg of pentaerythritol (12.00L of dehydrated toluene is used for dissolving into solution in advance), stirring at a constant speed, heating to 110 ℃, keeping the temperature, reacting for 1h, sampling and analyzing the mass fraction (-NCO%) of isocyanate groups (according to GB/T13941-92 by a di-n-butylamine-monohydrochloride titration method), wherein the NCO% is reduced along with the progress of the reaction, so as to determine the reaction degree, detecting once every half an hour, and judging that the reaction end point is reached when the difference of the detection results of two consecutive times is within the range of 0.1. And after the reaction is finished, continuously stirring at a constant speed, cooling to 40 ℃, discharging, and obtaining colorless or light yellow transparent liquid, namely the DEDI/PE prepolymer.
NMR analysis and detection were carried out on the DEDI/PE prepolymer prepared in this example,1H NMR(400MHz,CDCl3)1.12(t,24H,8×CH3),2.24(m,8H,4×CH2),2.71(m,8H,4×CH2),2.83(m,8H,4×CH2),4.23(m,8H,4×CH2),7.17(d,4H,4×CH),7.20(m,4H,4×CH),7.23(d,4H,4×CH),7.28(d,4H,4×CH),7.44(d,4H,4×CH),7.47(s,4H,4×CH),9.88(s,4H,4×NH)。
13C NMR(101MHz,CDCl3)11.25,11.25,11.25,11.25,21.33,21.33,21.33,21.33,36.45,36.45,36.45,36.45,36.49,36.49,36.49,36.49,58.95,58.95,58.95,58.95,70,69,118.57,118.57,118.57,118.57,121.13,121.13,121.13,121.13,122.03,122.03,122.03,122.03,124.52,124.52,124.52,124.52,126.53,126.53,126.53,126.53,129.97,129.97,129.97,129.97,130.04,130.04,130.04,130.04,130.75,130.75,130.75,130.75,132.82,132.82,132.82,132.82,133.06,133.06,133.06,133.06,134.49,134.49,134.49,134.49,135.77,135.77,135.77,135.77,136.68,136.68,136.68,136.68,152.29,152.29,152.29,152.29。
the product FT-IR (KBr pellet) was detected at 3250cm-1-3500cm-1(-NHCO cis NH stretching vibration), 2240cm-1-2280cm-1(-NCO characteristic absorption Peak), 1715cm-1-1750cm-1(amide I bond C ═ O), 1520cm-1-1560cm-1(amide II bond N-H deformation vibration) appears in 4 characteristic absorption peaks.
Through the above analysis, the product was a 2,2 '-diethyl-diphenylethane-4, 4' -diisocyanate/PE prepolymer.
The product Gel Permeation Chromatography (GPC) detected that the peak of the 2,2 '-diethyl-diphenylethane-4, 4' -diisocyanate/PE prepolymer is at 13.0min (the peak is at 20.5min of DEDI monomer), and the content (normalization method) is 90.0%.
Example 6
Adding 100.00L of dimethylbenzene into a reaction kettle, blowing nitrogen to remove moisture, adding 140.50kg of 2,2 '-di-n-propyl-diphenylethane-4, 4' -diisocyanate, introducing nitrogen for protection, heating to 60 ℃, adding 13.60kg of pentaerythritol (12.00L of dehydrated dimethylbenzene is used for dissolving into solution in advance), stirring at a constant speed, heating to 120 ℃, keeping the temperature, reacting for 1h, sampling and analyzing the mass fraction (-NCO%) of isocyanate groups (according to GB/T13941-92 by a di-n-butylamine-hydrochloric acid titration method), wherein the NCO% is reduced along with the progress of the reaction, so as to determine the reaction degree, detecting once every half an hour, and determining that the reaction end point is reached when the difference of the detection results of two consecutive times is within the range of 0.1. And after the reaction is finished, continuously stirring at a constant speed, cooling to 40 ℃, discharging, and obtaining colorless or light yellow transparent liquid, namely the DEDI/PE prepolymer.
NMR analysis and detection were carried out on the DEDI/PE prepolymer prepared in this example,1H NMR(400MHz,CDCl3)1.01(t,24H,8×CH3),2.11(m,8H,4×CH2),2.35(m,8H,4×CH2),2.70(m,8H,4×CH2),2.82(m,8H,4×CH2),4.22(m,8H,4×CH2),7.15(d,4H,4×CH),7.20(m,4H,4×CH),7.22(d,4H,4×CH),7.27(d,4H,4×CH),7.43(d,4H,4×CH),7.46(s,4H,4×CH),9.87(s,4H,4×NH)。
13C NMR(101MHz,CDCl3)9.93,9.93,9.93,9.93,15.54,15.54,15.54,15.54,22.31,22.31,22.31,22.31,36.43,36.43,36.43,36.43,36.47,36.47,36.47,36.47,58.93,58.93,58.93,58.93,70,67,118.55,118.55,118.55,118.55,121.11,121.11,121.11,121.11,122.01,122.01,122.01,122.01,124.50,124.50,124.50,124.50,126.51,126.51,126.51,126.51,129.95,129.95,129.95,129.95,130.02,130.02,130.02,130.02,130.73,130.73,130.73,130.73,132.80,132.80,132.80,132.80,133.04,133.04,133.04,133.04,134.47,134.47,134.47,134.47,135.75,135.75,135.75,135.75,136.66,136.66,136.66,136.66,152.31,152.31,152.31,152.31。
the product FT-IR (KBr pellet) was detected at 3250cm-1-3500cm-1(-NHCO cis NH stretching vibration), 2240cm-1-2280cm-1(-NCO characteristic absorption Peak), 1715cm-1-1750cm-1(amide I bond C ═ O), 1520cm-1-1560cm-1(amide II bond N-H deformation vibration) appears in 4 characteristic absorption peaks.
Through the above analysis, the product was 2,2 '-di-n-propyl-diphenylethane-4, 4' -diisocyanate/PE prepolymer.
The product Gel Permeation Chromatography (GPC) detected that the peak of the 2,2 '-di-n-propyl-diphenylethane-4, 4' -diisocyanate/PE prepolymer is at 13.1min (the peak is at 20.5min of DEDI monomer), and the content (normalization method) is 90.5%.
Example 7
Adding 90.00L of toluene into a reaction kettle, blowing nitrogen to remove water, adding 117.00kg of 3,3 '-dimethyl-diphenylethane-6, 6' -diisocyanate, introducing nitrogen for protection, heating to 60 ℃, adding 13.60kg of pentaerythritol (12.00L of dehydrated toluene is used for dissolving into solution in advance), stirring at a constant speed, heating to 90 ℃, carrying out heat preservation reaction for 1h, sampling and analyzing the mass fraction (-NCO%) of isocyanate groups (according to GB/T13941-92 by a di-n-butylamine-hydrochloric acid titration method), wherein the NCO% is reduced along with the progress of the reaction, so as to determine the reaction degree, detecting once every half an hour, and judging that the reaction end point is reached when the difference of the detection results of two consecutive times is within the range of 0.1. And after the reaction is finished, continuously stirring at a constant speed, cooling to 40 ℃, discharging, and obtaining colorless or light yellow transparent liquid, namely the DEDI/PE prepolymer.
NMR analysis and detection were carried out on the DEDI/PE prepolymer prepared in this example,1H NMR(400MHz,CDCl3)2.17(s,24H,8×CH3),2.65(m,8H,4×CH2),2.80(m,8H,4×CH2),4.27(m,8H,4×CH2),7.15(d,4H,4×CH),7.22(s,4H,4×CH),7.26(d,4H,4×CH),7.29(d,4H,4×CH),7.46(d,4H,4×CH),7.50(s,4H,4×CH),9.89(s,4H,4×NH)。
13C NMR(101MHz,CDCl3)18.92,18.92,18.92,18.92,19.15,19.15,19.15,19.15,36.50,36.50,36.50,36.50,36.54,36.54,36.54,36.54,58.95,58.95,58.95,58.95,70,77,118.47,118.47,118.47,118.47,121.15,121.15,121.15,121.15,122.15,122.15,122.15,122.15,124.57,124.57,124.57,124.57,126.56,126.56,126.56,126.56,129.97,129.97,129.97,129.97,130.02,130.02,130.02,130.02,130.74,130.74,130.74,130.74,132.87,132.87,132.87,132.87,133.09,133.09,133.09,133.09,134.51,134.51,134.51,134.51,135.79,135.79,135.79,135.79,136.74,136.74,136.74,136.74,152.31,152.31,152.31,152.31。
the product FT-IR (KBr pellet) was detected at 3250cm-1-3500cm-1(-NHCO cis NH stretching vibration), 2240cm-1-2280cm-1(-NCO characteristic absorption Peak), 1715cm-1-1750cm-1(amide I bond C ═ O), 1520cm-1-1560cm-1(amide II bond N-H deformation vibration) appears in 4 characteristic absorption peaks.
Through the above analysis, the product was a 3,3 '-dimethyl-diphenylethane-6, 6' -diisocyanate/PE prepolymer.
The product Gel Permeation Chromatography (GPC) detected that the 3,3 '-dimethyl-diphenylethane-6, 6' -diisocyanate/PE prepolymer showed a peak at 13.4min (DEDI monomer showed a peak at 20.5 min) and a content (normalized method) of 90.7%.
Corresponding DEDI/PE prepolymers can be prepared analogously to examples 1 to 7, using the appropriate starting materials diphenylethane diisocyanate.
Example 8Storage stability test of DEDI/PE prepolymer
The DEDI/PE prepolymer should be kept sealed and dry during storage, and placed in a cool and ventilated place without exposure to sunlight. To better investigate the influence of the storage time on the prepolymer, the-NCO mass fractions were measured at room temperature at different periods of 0h, 6h, 12h, 24h, 2d, 3d, 5d, 7d, 14d, 21d, 30d and 60d, respectively, and the corresponding DEDI monomers were used for comparison. The mass fraction of-NCO was measured by the di-n-butylamine hydrochloride titration method in accordance with GB/T13941-92, and the results are shown in Table 1.
TABLE 1 results of sample storage experiments
As can be seen from the results of the storage tests in Table 1, the mass fractions of-NCO in the case of diphenylethane diisocyanate and DEDI/PE prepolymer both decreased gradually with increasing storage time, the mass fraction of-NCO decreased sharply after 6 hours of DEDI storage, so that the storage life of diphenylethane diisocyanate was within 6 hours. The DEDI/PE prepolymer is stored for 60 days, the mass fraction of NCO is almost unchanged, and the storage time of the DEDI/PE prepolymer can reach at least 60 days. Thus, the storage time of the DEDI/PE prepolymer can be up to 60 days, the storage stability being 240 times that of DEDI.
Example 9DEDI/PE prepolymer polyurethane elastomer performance test
Polyurethane elastomer samples (DEDI-p01, DEDI-p02, DEDI-p03, DEDI-p04, DEDI-p05, DEDI-p06, DEDI-p07, TDI-p 01) were prepared by vacuum dehydrating 100.0g of polyester polyol (hydroxyl number 56, Shandong Dada) at 110 deg.C to less than 0.05% moisture, cooling to 80 deg.C, adding metered DEDI/PE prepolymers (isocyanate index 1.05), TDI/pentaerythritol (isocyanate index 1.05, control) and MDI/pentaerythritol (isocyanate index 1.05, control) such as DEDI/PE prepolymers such as example 1, example 2, example 3, example 4, example 5, example 6, and example 7, stirring uniformly, vacuum degassing, pouring into a mold, curing at 100 deg.C and curing and vulcanizing completely, and standing at room temperature for 7 days, MDI-p 01).
The performance test tests various performances according to the national standard: the test is carried out by testing hardness GB531-92, tensile strength GB528-98, elongation GB528-98 and tear strength GB 592-99. The results are summarized in Table 2.
TABLE 2 influence of DEDI/PE prepolymer type on elastomer Properties
Isocyanate index (equivalent of isocyanate component/equivalent of hydroxyl component) 1.05
As can be seen from the experimental results, (1) the DEDI/PE prepolymer elastomers (DEDI-p01, DEDI-p02, DEDI-p03, DEDI-p04, DEDI-p05, DEDI-p06 and DEDI-p07) have slightly higher hardness than TDI-p01 and MDI-p 01; (2) the elongation of the DEDI/PE prepolymer elastomer (DEDI-p01, DEDI-p02, DEDI-p03, DEDI-p04, DEDI-p05, DEDI-p06 and DEDI-p07) is greatly improved compared with that of TDI-p01 and MDI-p 01; (3) the tensile strength and the tear strength of the DEDI/PE prepolymer elastomers (DEDI-p01, DEDI-p02, DEDI-p03, DEDI-p04, DEDI-p05, DEDI-p06 and DEDI-p07) are improved to a certain extent compared with TDI-p01 and MDI-p 01.
Because of the chemical structure of the bis-phenylethane-CH2-CH2The modified product has a certain twistability, is modified by pentaerythritol to form a DEDI/PE prepolymer, and has the advantages of increased space resistance of the product, increased distance between molecules, reduced acting force between molecules and reduced NCO group activity. Compared with DEDI, the chemical structure is greatly different, making the composition diversified and amorphous.
Therefore, compared with the elastomer prepared from MDI and TDI, the elastomer prepared from the DEDI/PE prepolymer has greatly improved properties such as tensile strength, tear strength and the like.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A diphenyl ethane diisocyanate/pentaerythritol prepolymer is characterized in that the diphenyl ethane diisocyanate/pentaerythritol prepolymer has a structure shown in a formula (I),
wherein, R is1And R2Each independently selected from H and alkyl.
2. The diphenylethane diisocyanate/pentaerythritol prepolymer as defined in claim 1 wherein when R is1And R2When the substituents are the same, the compound is a cyclic compound,
the R is1At the C-2 or C-3 position of the diphenylethane group, the R2At the C-2 'or C-3' position of the diphenylethane group;
preferably, the alkyl group is C1-C6A linear or branched alkyl group; preferably C1-C3A linear or branched alkyl group;
preferably, the alkyl group is selected from methyl, ethyl and n-propyl;
preferably, the-NH-is located at the C-4, C-5 or C-6 position of the diphenylethane group and the-NCO is located at the C-4', C-5' or C-6' position of the diphenylethane group.
Preferably, R1At C-2 or C-3 position of the diphenylethane group and R1Is H or methyl or ethyl or n-propyl; r2At C-2 'or C-3' position of the diphenylethane group and R2Is H or methyl or ethyl or n-propyl; -NH-is in the C-4 or C-5 position of the diphenylethylene group; -NCO is located at the C-4 'or C-5' position of the diphenylethylene glycol group.
Further preferably, the diphenylethane diisocyanate/pentaerythritol prepolymer is selected from the following structures:
diphenylethane-4, 4' -diisocyanate/pentaerythritol prepolymer;
2,2 '-dimethyl-diphenylethane-4, 4' -diisocyanate/pentaerythritol prepolymer;
2,2 '-dimethyl-diphenylethane-5, 5' -diisocyanate/pentaerythritol prepolymer;
2,2 '-dimethyl-diphenylethane-6, 6' -diisocyanate/pentaerythritol prepolymer;
2,2 '-diethyl-diphenylethane-4, 4' -diisocyanate/pentaerythritol prepolymer;
2,2 '-di-n-propyl-diphenylethane-4, 4' -diisocyanate/pentaerythritol prepolymer;
3,3 '-dimethyl-diphenylethane-6, 6' -diisocyanate/pentaerythritol prepolymer.
3. The diphenylethane diisocyanate/pentaerythritol prepolymer as defined in claim 1 wherein when R is1And R2When the substituent group is different from the substituent group,
the R is1At the C-2 or C-3 position of the diphenylethane group, the R2At the C-2 'or C-3' position of the diphenylethane group;
preferably, the alkyl group is C1-C6A linear or branched alkyl group;
preferably, the alkyl group is C1-C3A linear or branched alkyl group;
preferably, the alkyl group is selected from methyl, ethyl and n-propyl;
preferably, the-NH-is located at the C-4, C-5 or C-6 position of the diphenylethane group and the-NCO is located at the C-4', C-5' or C-6' position of the diphenylethane group.
4. A preparation method of a diphenyl ethane diisocyanate/pentaerythritol prepolymer is characterized by comprising the steps of reacting diphenyl ethane diisocyanate and pentaerythritol as raw materials to prepare the diphenyl ethane diisocyanate/pentaerythritol prepolymer;
preferably, the preparation method comprises: dissolving diphenylethane diisocyanate in a solvent A, heating, adding pentaerythritol, stirring, heating and carrying out heat preservation reaction to obtain a reactant; after the reaction is judged to be finished, adding a solvent A, stirring, cooling and discharging to obtain liquid, namely the diphenyl ethane diisocyanate/pentaerythritol prepolymer;
the diphenylethane diisocyanate/pentaerythritol prepolymer as defined in any one of claims 1 to 3.
5. The method according to claim 4, wherein the diphenylethane diisocyanate is selected from the group consisting of diphenylethane-6, 6' -diisocyanate, diphenylethane-5, 5' -diisocyanate, diphenylethane-4, 4' -diisocyanate, 2' -dimethyldiphenylethane-6, 6' -diisocyanate, 2' -dimethyldiphenylethane-5, 5' -diisocyanate, 2' -dimethyldiphenylethane-4, 4' -diisocyanate, 2' -dimethyldiphenylethane-4, 5' -diisocyanate, 2' -dimethyldiphenylethane-4, 6' -diisocyanate, 2,2' -dimethyldiphenylethane-5, 6' -diisocyanate, 2' -diethyldiphenylethane-6, 6' -diisocyanate, 2' -ethylmethyldiphenylethane-5, 5' -diisocyanate, 2' -diethyldiphenylethane-4, 4' -diisocyanate, 2' -diethyldiphenylethane-4, 5' -diisocyanate, 2' -diethyldiphenylethane-4, 6' -diisocyanate, 2' -diethyldiphenylethane-5, 6' -diisocyanate, 2' -di-n-propyldiphenylethane-6, 6' -diisocyanate, 2' -di-n-propyldiphenylethane-5, 5' -diisocyanate, 2' -di-n-propyldiphenylethane-4, 4' -diisocyanate, 2' -di-n-propyldiphenylethane-4, 5' -diisocyanate, 2' -di-n-propyldiphenylethane-4, 6' -diisocyanate, 2' -di-n-propyldiphenylethane-5, 6' -diisocyanate, 3' -dimethyldiphenylethane-6, 6' -diisocyanate, 3' -dimethyldiphenylethane-5, 5' -diisocyanate, 3' -dimethyldiphenylethane-4, 4' -diisocyanate, 3' -diethyldiphenylethane-6, 6' -diisocyanate, and mixtures thereof, 3,3 '-diethyldiphenylethane-5, 5' -diisocyanate, 3 '-diethyldiphenylethane-4, 4' -diisocyanate, 3 '-di-n-propyldiphenylethane-6, 6' -diisocyanate, 3 '-di-n-propyldiphenylethane-5, 5' -diisocyanate, and 3,3 '-di-n-propyldiphenylethane-4, 4' -diisocyanate;
preferably, the solvent a is selected from inert solvents in which aromatic hydrocarbons are inactive;
preferably, the solvent a is selected from one or more of normal alkane, cyclohexane, benzene, toluene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, trichlorobenzene, sym-trichlorobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-xylene, m-xylene, p-xylene, hemimellitene, mesitylene, propylbenzene, ethyl acetate, n-propyl acetate, n-butyl acetate and benzyl acetate.
6. The production method according to claim 4, wherein the solvent A is an anhydrous solvent;
preferably, the amount of the solvent A is that the solvent A is dissolved in 0.05L-50L of solvent per kilogram of diphenylethane diisocyanate, and preferably 0.5L-2L;
preferably, the pentaerythritol is dissolved into a solution by using a solvent A in advance;
preferably, the molar ratio of diphenylethane diisocyanate to pentaerythritol is from 1.0 to 10.0: 1.0, preferably from 2.5 to 5.0: 1.0.
7. The preparation method according to claim 4, wherein the reaction is carried out under nitrogen protection;
preferably, the heating temperature is 0.0-200 ℃, preferably 50-100 ℃, and further preferably 60-80 ℃;
preferably, the heating and heat-preserving reaction temperature is 0.0-200 ℃, and preferably 60-120 ℃;
preferably, the heating and heat preservation reaction time is 0.5-2h, further 1 h;
preferably, the two times of stirring are uniform stirring;
preferably, the uniform stirring time is 15-45min, and further 30 min.
8. The production method according to claim 4, wherein the method of judging the completion of the reaction is: sampling and analyzing the quantity fraction of the isocyanate matrix after the reaction is carried out for a certain time at the temperature preservation, detecting once every half an hour, and judging that the isocyanate matrix reaches the reaction end point when the difference value of the detection results of two consecutive times is within 0.1;
preferably, the mass fraction of the isocyanate groups is 1.0% -50.0%, preferably 5.0% -30.0%;
preferably, the temperature is reduced to 30-50 ℃, further 40 ℃.
9. A polyurethane material prepared from the diphenylethane diisocyanate/pentaerythritol prepolymer according to claim 1 or 2.
10. Use of a process for the preparation of a diphenylethane diisocyanate/pentaerythritol as claimed in any of claims 1 to 3 or of a diphenylethane diisocyanate/pentaerythritol prepolymer as claimed in any of claims 4 to 8 in chemically synthesized polyurethanes.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US3833386A (en) * | 1972-07-07 | 1974-09-03 | Grace W R & Co | Method of prepairing porous ceramic structures by firing a polyurethane foam that is impregnated with inorganic material |
| JPS5083592A (en) * | 1973-11-29 | 1975-07-05 | ||
| US4816597A (en) * | 1983-10-02 | 1989-03-28 | New Jersey Institute Of Technology | Dental restorative materials based upon blocked isocyanates |
| US5153237A (en) * | 1991-09-09 | 1992-10-06 | Isp Investments Inc. | Radiation curable propenyl ether resins |
| US20050197451A1 (en) * | 2004-03-04 | 2005-09-08 | Basf Corporation | Acrylic composition and a curable coating composition including the same |
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