CN114044870A - Polyurethane chain extender and preparation method thereof, and casting polyurethane elastomer and preparation method thereof - Google Patents
Polyurethane chain extender and preparation method thereof, and casting polyurethane elastomer and preparation method thereof Download PDFInfo
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- CN114044870A CN114044870A CN202111458398.XA CN202111458398A CN114044870A CN 114044870 A CN114044870 A CN 114044870A CN 202111458398 A CN202111458398 A CN 202111458398A CN 114044870 A CN114044870 A CN 114044870A
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
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- 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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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
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- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
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Abstract
The invention discloses a polyurethane chain extender, a preparation method thereof, a casting polyurethane elastomer and a preparation method thereofThe preparation method comprises the following steps:
Description
Technical Field
The invention belongs to the technical field of polyurethane elastomers, and relates to a polyurethane chain extender and a preparation method thereof, and a casting polyurethane elastomer and a preparation method thereof.
Background
The casting polyurethane elastomer material is a new high polymer material, and has various physical properties due to various raw materials, different processing means, different soft-segment ratios in elastomer composition, different phase arrangements among molecular structures and the like, so that the application of the polyurethane elastomer material in some fields is greatly widened.
In the preparation process of the casting polyurethane elastomer, workers usually want to have enough long operation time for operation convenience, namely the viscosity of the mixed two active components can be kept in a low state for a long enough time for casting, so that low reactivity is required, but the final reaction degree is inevitably reduced, so that the mechanical property of the material cannot meet the use requirement, in order to solve the contradiction between the two aspects, in the actual use, people use aromatic amine chain extenders with high steric hindrance to reduce the reactivity, such as MOCA, DETDA and the like, but the chain extenders have strong carcinogenicity or strong corrosivity and irritation, and are not beneficial to the health of constructors; on the other hand, the casting body needs to be vulcanized at high temperature after being demoulded, which causes energy waste and reduction of production efficiency to a greater extent.
Patent CN104448196A, CN111072901A, etc. all disclose the use of MOCA as a chain extender, but this method still requires high temperature and long time aging to obtain polyurethane casting with desired properties, consumes energy while prolonging production time, and is toxic and highly corrosive because the chain extender contains aromatic amine.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a polyurethane chain extender and a preparation method thereof, wherein the chain extender contains abundant acylamino, can form hydrogen bonds with hydroxyl groups to be associated, so that the reaction is slow, the sufficient operation time is ensured, and meanwhile, the abundant carbonyl groups provide strong and tough bridging points for the formation of the hydrogen bonds, so that the final mechanical property of the material is greatly improved. In addition, the existence of aromatic ketone groups in molecules enables the material to be free degraded under the irradiation of ultraviolet light, and the material is an environment-friendly material. The chain extender does not contain aromatic primary amine in molecules, and has no carcinogenicity and irritation.
Another object of the present invention is to provide a cast polyurethane elastomer comprising the above polyurethane chain extender and a method for preparing the same.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
on the one hand, the invention provides a polyurethane chain extender, which has a structure shown in a formula I:
in formula I: r1、R2Each independently selected from H or C1-C6 alkyl, preferably H or C1-C3 alkyl; the R is1、R2May be the same or different.
The invention also provides a preparation method of the polyurethane chain extender shown in the formula I, which is prepared by reacting a compound shown in the formula II with a compound shown in the formula III;
in the formula II R2In the formula III, R1And R in formula I1、R2Are identical, i.e. R1、R2Each independently selected from H or C1-C6 alkyl, preferably H or C1-C3 alkyl(ii) a The R is1、R2May be the same or different.
Preferably, the compound shown in the formula II is selected from ethylene carbonate, propylene carbonate, ethylene carbonate and styrene carbonate, and more preferably ethylene carbonate and propylene carbonate.
Preferably, the compound of formula III is selected from 4,4 '-diaminobenzophenone, 4' -bis (methylamino) benzophenone.
In the preparation method, the mol ratio of the compound shown in the formula II to the compound shown in the formula III is 1.9-2.1: 1, preferably 1.95-2.05: 1.
in the preparation method, the reaction is carried out at the temperature of 50-100 ℃, preferably at the temperature of 55-90 ℃ for 0.5-4h, preferably 1.5-3 h.
The polyurethane chain extender provided by the invention contains abundant acylamino, can form hydrogen bonds with hydroxyl groups to be associated, slows down the reaction rate and prolongs the operation time. The carbonyl provides a strong bridging point for the formation of hydrogen bonds, and the polyurethane cast elastomer with excellent mechanical properties can be obtained without long-time high-temperature vulcanization, so that the energy consumption is greatly reduced, and the production efficiency is improved. The aromatic ketone structure can degrade the polyurethane elastomer under the irradiation of ultraviolet light, and can be used for preparing environment-friendly novel environment-friendly materials.
The polyurethane chain extender shown in the formula I can be applied to the fields of preparation of casting polyurethane elastomers, spraying of polyurea and the like, and has the advantages of long operation time, high strength, degradability and the like.
The invention also provides a casting polyurethane elastomer, which comprises the following raw materials of a polyurethane chain extender shown in the formula I, preferably, the casting polyurethane elastomer comprises the following components in parts by mass:
aliphatic isocyanate prepolymer HC-10050-60 parts, preferably 55-60 parts;
40-50 parts of polyurethane chain extender, preferably 40-45 parts.
The aliphatic isocyanate prepolymer HC-100 is prepared by the reaction of polyether polyol and aliphatic diisocyanate;
preferably, the mass ratio of the polyether polyol to the aliphatic diisocyanate is 1: 1.5-2.5, preferably 1: 1.8-2.4.
Preferably, the polyether polyol has a molecular weight of 300-4000 and a functionality of 2-4, and is selected from any one or a combination of at least two of GE-204, RA-640, NT-403A, DV-125, MN-500, MN-700, MN-1000, MN-1500, MN-3050D, GE-303, more preferably any one or a combination of at least two of MN-700, MN-1000, MN-1500.
Preferably, the aliphatic diisocyanate is selected from any one or a combination of at least two of 1, 6-Hexamethylene Diisocyanate (HDI), HDI trimer, HDI biuret, 3-isocyanatomethylene-3, 5, 5-trimethylcyclohexyl isocyanate (IPDI), 4,4' -dicyclohexylmethane diisocyanate (HMDI), m-Xylylene Diisocyanate (XDI), Hydrogenated Xylylene Diisocyanate (HXDI), 2, 4-and 2,4, 4-trimethyl-1, 6-hexamethylene diisocyanate mixture (TMHMDI), tetramethyl m-xylylene diisocyanate (m-TMXDI), norbornane diisocyanate (NBDI), more preferably 1, 6-Hexamethylene Diisocyanate (HDI), 4,4' -dicyclohexylmethane diisocyanate (HMDI), m-Xylylene Diisocyanate (XDI), Hydrogenated Xylylene Diisocyanate (HXDI), 3-isocyanatomethylene-3, 5, 5-trimethylcyclohexyl isocyanate (IPDI).
The method for preparing the aliphatic isocyanate prepolymer by the prepolymerization reaction of the polyether polyol and the aliphatic diisocyanate is well known in the art, and the method has no special requirement, and can be prepared by any available method disclosed by the technical personnel. In some examples of the invention, the preparation steps that may be employed are: mixing polyether polyol and aliphatic diisocyanate, and reacting at 70-90 ℃, preferably 75-85 ℃ for 3-6h, preferably 3.5-5h to obtain the aliphatic isocyanate prepolymer HC-100.
The invention also provides a preparation method of the casting polyurethane elastomer, which comprises the following steps: heating and vacuumizing aliphatic isocyanate prepolymer HC-100, adding polyurethane chain extender, uniformly mixing, vacuumizing again, pouring into a mold coated with a release agent in advance, putting into a blowing oven at 90-110 ℃ for reaction for 20-50min, and demolding to obtain the cast polyurethane elastomer.
Preferably, when the aliphatic isocyanate prepolymer HC-100 is heated and vacuumized, the vacuum degree is 50-200Pa, the temperature is 80-130 ℃, preferably 90-110 ℃, and the time is 10-50min, preferably 20-30 min;
adding polyurethane chain extender, mixing, and vacuumizing again at the vacuum degree of 50-200Pa, the temperature of 80-130 ℃, preferably 90-110 ℃ for 1-3 min;
preferably, the reaction is carried out at a temperature of preferably 100 ℃ to 105 ℃ for a time of preferably 30 to 40 min.
The casting polyurethane elastomer has the advantages of long operation time, high strength, degradability and the like, and can be applied to the fields of sealing gaskets, printing rubber rollers, cleaning scraping sheets, rail protection and the like. Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
the invention provides a polyurethane chain extender which has long operation time and does not need post-curing, the chain extender has no corrosivity and irritation, and the aromatic ketone group in the chain extender can lead the material to be photodegraded under the irradiation of ultraviolet light, so the polyurethane chain extender is an environment-friendly polyurethane chain extender and is particularly suitable for preparing cast polyurethane elastomers.
Detailed Description
The present invention is further illustrated by the following specific examples, but the present invention is not limited to the following examples.
< sources of raw materials >
Propylene carbonate: shandongsenjie cleaning science and technology, Inc.;
ethylene carbonate, ethylene carbonate: Sigma-Aldrich Sigma Aldrich (Shanghai) trade, Inc.;
4,4' -diaminobenzophenone: suchengcheng chemical technology, Inc.;
4,4' -bis (methylamino) benzophenone: beijing Bailingwei science and technology Co., Ltd;
polyether polyol MN-500: shandong Lanxingdao Co., Ltd;
IPDI, HMDI, XDI: vanhua chemical group, Inc.;
MN-500, MN-100, MN-1500: shandong Lanxingdao Co., Ltd;
GE-204: the Shanghai Gaoqiao petrochemical industry;
3,3 '-dichloro-4, 4' -diaminodiphenylmethane (MOCA), filial sensation profound chemical Co., Ltd;
4,4' -dihydroxybenzophenone: Sigma-Aldrich Sigma Aldrich (Shanghai) trade, Inc.;
all other components are common commercial raw materials unless otherwise specified.
< methods for Performance test >
The operation time is as follows: mixing the chain extender with the polyurethane prepolymer, vacuumizing, testing the viscosity change at 25 ℃, and determining the time when the viscosity rises to two times of the initial viscosity as the operation time.
Tensile strength: GB/T1040.1-2006 determination of the tensile properties of plastics.
Degradation rate: preparing a polyurethane film with the size of 3cm x 150um, placing the film in the sun for 300h, and testing the weight loss rate of the film.
Nuclear magnetic hydrogen spectrum test: bruker AVANCEIII NMR spectrometer, 400MHz, solvent DMSO-d6, non-quantitative hydrogen spectrum conditions: 400.13MHz, ns-16, pulse sequence zg 30.
Example 1
Preparation of polyurethane chain extender A:
102g (1mol) of propylene carbonate is heated to 50 ℃, 106.25g (0.5mol) of 4,4' -diaminobenzophenone is added, and the reaction is carried out for 4 hours at 50 ℃ to obtain the polyurethane chain extender A.
By nuclear magnetic hydrogen spectroscopy analysis: the primary amine hydrogen displacement at 6.27nm disappears, secondary amine hydrogen displacement appears at 9.15nm, and hydroxyl displacement appears at 3.58 nm, which shows that the propylene carbonate reacts with 4,4' -diaminobenzophenone, and the chain extender A has the following structure:
example 2
Preparation of polyurethane chain extender B:
92.4g (1.05mol) of ethylene carbonate is heated to 100 ℃, 106.25g (0.5mol) of 4,4' -diaminobenzophenone is added, and the reaction is carried out for 1.5h at 100 ℃, thus obtaining the polyurethane chain extender B.
By nuclear magnetic hydrogen spectroscopy analysis: the primary amine hydrogen displacement at 6.27nm disappears, the secondary amine hydrogen displacement appears at 9.15nm, and meanwhile, the hydroxyl displacement appears at 3.65 nm, which shows that the ethylene carbonate reacts with 4,4' -diaminobenzophenone, and the chain extender B has the following structure:
example 3
Preparation of polyurethane chain extender C:
108.3g (0.95mol) of ethylene carbonate is heated to 70 ℃, 120.5g (0.5mol) of 4,4' -bis (methylamino) benzophenone is added, and the reaction is carried out for 3 hours at 70 ℃, thus obtaining the polyurethane chain extender C.
By nuclear magnetic hydrogen spectroscopy analysis: the secondary amine hydrogen shift at 4.07nm disappeared while the hydroxyl shift at 2.80 appeared, indicating that ethylene carbonate reacted with 4-4' dimethylaminobenzophenone and that chain extender C had the structure shown below:
example 4
Preparation of aliphatic isocyanate prepolymer HC-100: mixing 30g of polyether polyol MN-500 and 70g of IPDI, and reacting at 70 ℃ for 6h to obtain an aliphatic isocyanate prepolymer HC-100;
preparing a high-strength casting polyurethane elastomer:
weighing 50g of aliphatic isocyanate prepolymer HC-100, heating to 110 ℃, vacuumizing for 30min under the vacuum degree of 50Pa, adding 50g of polyurethane chain extender A prepared in the embodiment 1, stirring uniformly, vacuumizing for 1min under the temperature of 110 ℃ and the vacuum degree of 50Pa, pouring into a mold coated with a release agent in advance, putting into a blast oven at 100 ℃, reacting for 30min, and demolding to obtain the high-strength cast polyurethane elastomer.
The results of the performance tests are shown in Table 1.
Example 5
Preparation of aliphatic isocyanate prepolymer HC-100: mixing 35gGE-204 and 65g HMDI, and reacting at 75 ℃ for 4h to obtain an aliphatic isocyanate prepolymer HC-100;
preparing a high-strength casting polyurethane elastomer:
weighing 55g of aliphatic isocyanate prepolymer HC-100, heating to 100 ℃, vacuumizing for 30min under the vacuum degree of 100Pa, adding 45g of polyurethane chain extender B prepared in the embodiment 2, stirring uniformly, vacuumizing for 2min under the temperature of 100 ℃ and the vacuum degree of 100Pa, pouring into a mold coated with a release agent in advance, putting into a blast oven at 100 ℃, reacting for 35min, and demolding to obtain the high-strength cast polyurethane elastomer.
The results of the performance tests are shown in Table 1.
Example 6
Preparation of aliphatic isocyanate prepolymer HC-100: mixing 40gMN-1000 g and 60g XDI, and reacting for 5h at 80 ℃ to obtain an aliphatic isocyanate prepolymer HC-100;
preparing a high-strength casting polyurethane elastomer:
weighing 55g of aliphatic isocyanate prepolymer HC-100, heating to 110 ℃, vacuumizing for 20min under the vacuum degree of 200Pa, adding 45g of polyurethane chain extender C prepared in the embodiment 3, stirring uniformly, vacuumizing for 3min under the temperature of 110 ℃ and the vacuum degree of 200Pa, pouring into a mold coated with a release agent in advance, putting into a blast oven at 105 ℃, reacting for 30min, and demolding to obtain the high-strength cast polyurethane elastomer.
The results of the performance tests are shown in Table 1.
Comparative example 1
The method of example 4 is referred to, except that: the polyurethane chain extender A prepared in the example 1 is replaced by a polyurethane chain extender MOCA with equal mass, and other operations and parameters are not changed, so that the casting polyurethane elastomer is prepared.
The results of the performance tests are shown in Table 1.
Comparative example 2
The method of example 4 is referred to, except that: the polyurethane chain extender A prepared in example 1 was replaced with 4,4' -dihydroxybenzophenone of equal mass, and other operations and parameters were unchanged to prepare a cast polyurethane elastomer.
The results of the performance tests are shown in Table 1.
Comparative example 3
The method of example 4 is referred to, except that: the polyurethane chain extender A prepared in example 1 was replaced with 4,4' -diaminobenzophenone of equal mass, and other operations and parameters were unchanged to prepare a cast polyurethane elastomer.
The results of the performance tests are shown in Table 1.
TABLE 1 results of the Performance test of the polyurethane elastomers prepared in examples 4 to 6 and comparative examples 1 to 3
Claims (10)
1. A polyurethane chain extender is characterized in that the structure is shown as formula I:
in formula I: r1、R2Each independently selected from H or C1-C6 alkyl, preferably H or C1-C3 alkyl; the R is1、R2May be the same or different.
2. A method for preparing the polyurethane chain extender as claimed in claim 1, which is characterized in that the polyurethane chain extender is prepared by reacting a compound shown as a formula II with a compound shown as a formula III;
in the formula II R2In the formula III, R1And R in formula I1、R2The same is true.
3. The preparation method according to claim 2, wherein the compound represented by the formula II is selected from ethylene carbonate, propylene carbonate, ethylene carbonate and styrene carbonate, preferably ethylene carbonate and propylene carbonate; and/or
The compound shown in the formula III is selected from 4,4 '-diaminobenzophenone and 4,4' -di (methylamino) benzophenone.
4. The process according to claim 2 or 3, wherein the molar ratio of the compound of formula II to the compound of formula III is from 1.9 to 2.1: 1, preferably 1.95-2.05: 1.
the reaction is carried out at 50-100 deg.C, preferably 55-90 deg.C, for 0.5-4h, preferably 1.5-3 h.
5. Use of the polyurethane chain extender of claim 1 or prepared by the process of any one of claims 2 to 4 in the field of cast polyurethane elastomers, spray polyurea.
6. A casting polyurethane elastomer is characterized in that a polyurethane chain extender in claim 1 or prepared by the method in any one of claims 2 to 4 is included in raw materials, and preferably, the casting polyurethane elastomer comprises the following components in parts by mass:
aliphatic isocyanate prepolymer HC-10050-60 parts, preferably 55-60 parts;
40-50 parts of polyurethane chain extender, preferably 40-45 parts.
7. The cast polyurethane elastomer according to claim 6, wherein the aliphatic isocyanate prepolymer HC-100 is prepared by reacting a polyether polyol with an aliphatic diisocyanate;
preferably, the mass ratio of the polyether polyol to the aliphatic diisocyanate is 1: 1.5-2.5, preferably 1: 1.8-2.4.
8. The cast polyurethane elastomer as claimed in claim 6 or 7, wherein the polyether polyol has a molecular weight of 300-4000 and a functionality of 2-4, and is selected from any one or a combination of at least two of GE-204, RA-640, NT-403A, DV-125, MN-500, MN-700, MN-1000, MN-1500, MN-3050D, GE-303, preferably any one or a combination of at least two of MN-700, MN-1000, MN-1500;
the aliphatic diisocyanate is selected from 1, 6-hexamethylene diisocyanate, HDI trimer, HDI biuret, 3-isocyanatomethylene-3, 5, 5-trimethylcyclohexyl isocyanate, 4,4 '-dicyclohexylmethane diisocyanate, m-xylylene diisocyanate, hydrogenated xylylene diisocyanate, 2, 4-and 2,4, 4-trimethyl-1, 6-hexamethylene diisocyanate mixture, tetramethyl m-xylylene diisocyanate and norbornane diisocyanate, and is preferably at least one of 1, 6-hexamethylene diisocyanate, 4,4' -dicyclohexylmethane diisocyanate, m-xylylene diisocyanate, hydrogenated xylylene diisocyanate, HDI diisocyanate, m-xylylene diisocyanate, hydrogenated xylylene diisocyanate, p-xylylene diisocyanate, and mixtures thereof, At least one of 3-isocyanatomethylene-3, 5, 5-trimethylcyclohexyl isocyanate or the combination of at least two of the 3-isocyanatomethylene-3, 5, 5-trimethylcyclohexyl isocyanate;
preferably, the preparation method of the aliphatic isocyanate prepolymer HC-100 comprises the following steps: mixing polyether polyol and aliphatic diisocyanate, and reacting at 70-90 deg.C, preferably 75-85 deg.C for 3-6 hr, preferably 3.5-5 hr.
9. A method for preparing a cast polyurethane elastomer according to any one of claims 6 to 8, comprising the steps of: heating and vacuumizing aliphatic isocyanate prepolymer HC-100, adding polyurethane chain extender, uniformly mixing, vacuumizing again, pouring into a mold coated with a release agent in advance, putting into a blowing oven at 90-110 ℃ for reaction for 20-50min, and demolding to obtain the cast polyurethane elastomer.
10. The preparation method of the casting polyurethane elastomer according to claim 9, wherein when the aliphatic isocyanate prepolymer HC-100 is heated and vacuumized, the vacuum degree is 50-200Pa, the temperature is 80-130 ℃, preferably 90-110 ℃, and the time is 10-50min, preferably 20-30 min;
adding a polyurethane chain extender, mixing, and then vacuumizing again, wherein the vacuum degree is 50-200Pa, the temperature is 80-130 ℃, preferably 90-110 ℃, and the time is 1-3 min;
preferably, the reaction is carried out at the temperature of 100-105 ℃ for 30-40 min.
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