CN114044870B - Polyurethane chain extender and preparation method thereof, and cast polyurethane elastomer and preparation method thereof - Google Patents
Polyurethane chain extender and preparation method thereof, and cast polyurethane elastomer and preparation method thereof Download PDFInfo
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- CN114044870B CN114044870B CN202111458398.XA CN202111458398A CN114044870B CN 114044870 B CN114044870 B CN 114044870B CN 202111458398 A CN202111458398 A CN 202111458398A CN 114044870 B CN114044870 B CN 114044870B
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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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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- C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups
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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
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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 and a preparation method thereof, and a casting polyurethane elastomer and a preparation method thereof, wherein the structure of the polyurethane chain extender is shown as a formula I:
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 an emerging high polymer material, and has various physical properties due to various raw materials, different processing means, different soft and hard segment proportions in elastomer composition, different phase arrangement 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 pouring polyurethane elastomer, for the convenience of operation, workers often want a long enough operation time, namely, the viscosity of the two active components can be kept low for a long enough time after being mixed so as to facilitate pouring, thus the lower reactivity is required, but the final reaction degree is inevitably reduced, the mechanical properties of the material cannot meet the use requirement, and in order to solve the contradiction between the two aspects, on one hand, people use high-steric hindrance aromatic amine chain extenders to reduce the reactivity, such as MOCA, DETDA and the like, but the chain extenders have stronger carcinogenicity or stronger corrosiveness and irritation and are unfavorable for the health of constructors; on the other hand, the casting body needs to be vulcanized at a high temperature after being demolded, so that the energy waste and the reduction of the production efficiency are caused to a great extent.
Patent CN104448196a, CN111072901a, etc. all disclose the use of MOCA as a chain extender, but the process still requires curing at high temperature and for a long time to obtain polyurethane casting with the desired properties, consumes energy and also prolongs the production time, and because the chain extender contains aromatic amine, it is toxic and highly corrosive.
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 rich amide groups, can form hydrogen bond association with hydroxyl groups, so that the reaction is slow, the sufficient operation time is ensured, and meanwhile, the rich carbonyl groups provide a strong bridging point for the formation of the hydrogen bonds, so that the final mechanical property of the material is greatly improved. In addition, the existence of aryl ketone groups in the molecules enables the material to be freely degraded under the irradiation of ultraviolet light, so that the material is an environment-friendly material. And the chain extender does not contain aromatic primary amine in the molecule, and has no carcinogenicity and irritation.
Another object of the present invention is to provide a cast polyurethane elastomer comprising the polyurethane chain extender as described above and a method for preparing the same.
In order to achieve the above object, the present invention has the technical scheme that:
in one aspect, the invention provides a polyurethane chain extender, the structure of which is shown as formula I:
in formula I: r is R 1 、R 2 Each independently selected from H or C1-C6 alkyl, preferably H or C1-C3 alkyl; the R is 1 、R 2 May 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;
r in II 2 R in III 1 With R in formula I 1 、R 2 Identical, i.e. R 1 、R 2 Each independently selected from H or C1-C6 alkyl, preferably H or C1-C3 alkyl; the R is 1 、R 2 May be the same or different.
Preferably, the compound of formula II is selected from the group consisting of ethylene carbonate, propylene carbonate, ethylene carbonate, styrene carbonate, more preferably ethylene carbonate, propylene carbonate.
Preferably, the compound of formula III is selected from the group consisting of 4,4 '-diaminobenzophenone, 4' -di (methylamino) benzophenone.
In the preparation method, the molar 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 of the invention, the reaction is carried out at 50-100 ℃, preferably 55-90 ℃ for 0.5-4 hours, preferably 1.5-3 hours.
The polyurethane chain extender provided by the invention contains rich amide groups, can form hydrogen bond association with hydroxyl groups, slows down the reaction rate and prolongs the operation time. The carbonyl provides a strong bridging point for the formation of hydrogen bonds, and polyurethane casting 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 ultraviolet irradiation, and can be used for preparing novel environment-friendly materials.
The polyurethane chain extender shown in the formula I can be applied to the fields of preparation of casting polyurethane elastomer, spray 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 polyurethane chain extender shown in the formula I, preferably, the polyurethane chain extender comprises the following components in parts by mass:
50-60 parts, preferably 55-60 parts, of aliphatic isocyanate prepolymer HC-100;
40-50 parts, preferably 40-45 parts, of polyurethane chain extender.
The aliphatic isocyanate prepolymer HC-100 is prepared by reacting polyether polyol with 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-403-A, DV-125, MN-500, MN-700, MN-1000, MN-1500, MN-3050-D, 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 at least one of 1, 6-Hexamethylene Diisocyanate (HDI), HDI trimer, HDI biuret, 3-isocyanatomethylene-3, 5-trimethylcyclohexyl isocyanate (IPDI), 4 '-dicyclohexylmethane diisocyanate (HMDI), m-Xylylene Diisocyanate (XDI), hydrogenated Xylylene Diisocyanate (HXDI), 2, 4-and 2, 4-trimethyl-1, 6-hexamethylene diisocyanate mixture (TMHMDI), tetramethyl m-xylylene diisocyanate (m-TMXDI), norbornane diisocyanate (NBDI) or a combination of at least two, more preferably at least one of 1, 6-Hexamethylene Diisocyanate (HDI), 4' -dicyclohexylmethane diisocyanate (HMDI), m-Xylylene Diisocyanate (XDI), hydrogenated Xylylene Diisocyanate (HXDI), 3-isocyanatomethylene-3, 5-trimethylcyclohexyl isocyanate (IPDI) or a combination of at least two thereof.
The method of the invention 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 is not particularly required, and the technical personnel can prepare the prepolymer by any implementation mode disclosed in the prior art. In some examples of the invention, the preparation steps that may be employed are: the aliphatic isocyanate prepolymer HC-100 is prepared by mixing a polyether polyol with an aliphatic diisocyanate and reacting at 70-90 ℃, preferably 75-85 ℃ for 3-6 hours, preferably 3.5-5 hours.
The invention also provides a preparation method of the casting polyurethane elastomer, which comprises the following steps: heating and vacuumizing the aliphatic isocyanate prepolymer HC-100, adding the polyurethane chain extender, uniformly mixing, vacuumizing again, pouring into a die which is coated with a release agent in advance, placing into a blast oven at 90-110 ℃ for reacting for 20-50min, and demoulding to obtain the casting polyurethane elastomer.
Preferably, when the temperature of the aliphatic isocyanate prepolymer HC-100 is increased and the vacuum is pumped, the vacuum degree is 50-200Pa, the temperature is 80-130 ℃, preferably 90-110 ℃ and the time is 10-50min, preferably 20-30min;
adding polyurethane chain extender, mixing, and vacuumizing again, wherein the vacuum degree is 50-200Pa, the temperature is 80-130 ℃, preferably 90-110 ℃, and the time is 1-3min;
preferably, the reaction is carried out at a temperature of preferably 100-105℃for a time of preferably 30-40min.
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 blades, 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, is not corrosive and irritant, and can lead the material to be photodegradation under the irradiation of ultraviolet light by an aryl ketone group, thereby being an environment-friendly polyurethane chain extender and being particularly suitable for the preparation of a pouring polyurethane elastomer.
Detailed Description
The present invention will be further illustrated by the following specific examples, but the present invention is not limited to the following examples.
< source of Main Material >
Propylene carbonate: shandong Senjie cleaning technology Co., ltd;
ethylene carbonate, ethylene carbonate: sigma-Aldrich Sigma Aldrich (Shanghai) trade Co., ltd;
4,4' -diaminobenzophenone: salt city forward chemical technology limited;
4,4' -bis (methylamino) benzophenone: beijing carboline technologies Co., ltd;
polyether polyol MN-500: shandong blue Star Dong Co., ltd;
IPDI, HMDI, XDI: wanhua chemical group Co., ltd;
MN-500, MN-100, MN-1500: shandong blue Star Dong Co., ltd;
GE-204: the Shanghai Gao Qiao is petrochemical;
3,3 '-dichloro-4, 4' -diaminodiphenylmethane (MOCA) a company of the filial sense deep chemical Co., ltd;
4,4' -dihydroxybenzophenone: sigma-Aldrich Sigma Aldrich (Shanghai) trade Co., ltd;
the other materials are common commercial materials unless otherwise specified.
< Performance test method >
Operating time: and mixing the chain extender with the polyurethane prepolymer, vacuumizing, and testing the viscosity change at 25 ℃ to obtain the operation time when the viscosity rises to twice the initial viscosity.
Tensile strength: GB/T1040.1-2006 determination of Plastic tensile Properties.
Degradation rate: polyurethane films were prepared with dimensions of 3cm x 150um and placed under sunlight for 300h to test the film weight loss rate.
Nuclear magnetic hydrogen spectrum test: bruker AVANCEIII nuclear magnetic resonance spectrometer, 400MHz, solvent DMSO-d6, non-quantitative hydrogen spectrum conditions: 400.13mhz, ns=16, pulse train zg30.
Example 1
Preparation of polyurethane chain extender A:
102g (1 mol) of propylene carbonate was heated to 50℃and 106.25g (0.5 mol) of 4,4' -diaminobenzophenone was added thereto to react at 50℃for 4 hours to give polyurethane chain extender A.
By nuclear magnetic hydrogen spectrometry: the primary amine hydrogen shift at 6.27nm disappeared, the secondary amine hydrogen shift at 9.15nm appeared, and the hydroxyl shift at 3.58 appeared, indicating that propylene carbonate reacted with 4,4' -diaminobenzophenone, and chain extender a had the structure shown below:
example 2
Preparation of polyurethane chain extender B:
92.4g (1.05 mol) of ethylene carbonate was heated to 100℃and 106.25g (0.5 mol) of 4,4' -diaminobenzophenone was added thereto and reacted at 100℃for 1.5 hours to give a polyurethane chain extender B.
By nuclear magnetic hydrogen spectrometry: the primary amine hydrogen displacement at 6.27nm disappeared, the secondary amine hydrogen displacement at 9.15nm appeared, and the hydroxyl displacement at 3.65 appeared, indicating that the reaction of ethylene carbonate with 4,4' -diaminobenzophenone took place, and chain extender B had the structure shown below:
example 3
Preparation of polyurethane chain extender C:
108.3g (0.95 mol) of ethylene carbonate was heated to 70℃and 120.5g (0.5 mol) of 4,4' -bis (methylamino) benzophenone was added thereto to react at 70℃for 3 hours to give polyurethane chain extender C.
By nuclear magnetic hydrogen spectrometry: 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: 30g of polyether polyol MN-500 and 70g of IPDI are mixed and reacted for 6 hours at 70 ℃ to obtain 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 condition of the vacuum degree of 50Pa, adding 50g of polyurethane chain extender A prepared in example 1, uniformly stirring, vacuumizing for 1min under the condition of the temperature of 110 ℃ and the vacuum degree of 50Pa again, pouring into a die with a pre-coated release agent, putting into a blast oven with the temperature of 100 ℃, reacting for 30min, and demoulding to obtain the high-strength pouring polyurethane elastomer.
The results of the performance test are shown in Table 1.
Example 5
Preparation of aliphatic isocyanate prepolymer HC-100: mixing 35gGE-204 and 65g HMDI, and reacting for 4 hours at 75 ℃ to obtain 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 at the vacuum degree of 100Pa, adding 45g of polyurethane chain extender B prepared in example 2, uniformly stirring, vacuumizing for 2min at the temperature of 100 ℃ and the vacuum degree of 100Pa again, pouring into a die with a pre-coated release agent, putting into a blast oven at the temperature of 100 ℃, reacting for 35min, and demoulding to obtain the high-strength casting polyurethane elastomer.
The results of the performance test are shown in Table 1.
Example 6
Preparation of aliphatic isocyanate prepolymer HC-100: mixing 40g gMN-1000 g XDI and reacting at 80 ℃ for 5h to obtain 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 at the vacuum degree of 200Pa, adding 45g of polyurethane chain extender C prepared in example 3, uniformly stirring, vacuumizing for 3min at the temperature of 110 ℃ and the vacuum degree of 200Pa again, pouring into a die with a pre-coated release agent, putting into a blast oven at 105 ℃, reacting for 30min, and demoulding to obtain the high-strength casting polyurethane elastomer.
The results of the performance test are shown in Table 1.
Comparative example 1
The process of example 4 differs only in that: the polyurethane chain extender A prepared in example 1 is replaced by a polyurethane chain extender MOCA with equal quality, and other operations and parameters are unchanged, so that the casting polyurethane elastomer is prepared.
The results of the performance test are shown in Table 1.
Comparative example 2
The process of example 4 differs only in that: the polyurethane chain extender A prepared in example 1 was replaced with equal mass of 4,4' -dihydroxybenzophenone, and other operations and parameters were unchanged, to prepare a cast polyurethane elastomer.
The results of the performance test are shown in Table 1.
Comparative example 3
The process of example 4 differs only in 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 test are shown in Table 1.
TABLE 1 results of Performance test of polyurethane elastomer prepared in examples 4-6 and comparative examples 1-3
Claims (23)
1. A polyurethane chain extender is characterized in that the structure is shown as a formula I:
in formula I: r is R 1 、R 2 Each independently selected from H or C1-C6 alkyl, said R 1 、R 2 May be the same or different.
2. The polyurethane chain extender of claim 1, wherein in formula i: r is R 1 、R 2 Each independently selected from H or C1-C3 alkyl.
3. A method for preparing the polyurethane chain extender as claimed in claim 1 or 2, which is characterized in that the polyurethane chain extender is prepared by reacting a compound shown in a formula II with a compound shown in a formula III;
r in II 2 R in III 1 With R in formula I 1 、R 2 The same applies.
4. The process according to claim 3, wherein the compound of formula II is selected from the group consisting of 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.
5. The process according to claim 3, wherein the molar ratio of the compound of formula II to the compound of formula III is 1.9-2.1:1, a step of;
the reaction is carried out at 50-100 ℃ for 0.5-4h.
6. The process according to claim 5, wherein the molar ratio of the compound of formula II to the compound of formula III is 1.95-2.05:1.
7. the process according to claim 5, wherein the reaction is carried out at a temperature of 55 to 90℃for a period of 1.5 to 3 hours.
8. Use of the polyurethane chain extender of claim 1 or 2 or prepared by the process of any one of claims 3 to 7 in the field of cast polyurethane elastomers, spray polyurea.
9. A cast polyurethane elastomer, characterized in that the polyurethane chain extender of claim 1 or 2 or prepared by the method of any one of claims 3-7 is included in raw materials, and the composition of the polyurethane chain extender in parts by mass includes:
50-60 parts of aliphatic isocyanate prepolymer HC-100;
40-50 parts of polyurethane chain extender.
10. The cast polyurethane elastomer according to claim 9, wherein the composition in parts by mass comprises:
55-60 parts of aliphatic isocyanate prepolymer HC-100;
40-45 parts of polyurethane chain extender.
11. The cast polyurethane elastomer of claim 9, wherein the aliphatic isocyanate prepolymer HC-100 is prepared by reacting a polyether polyol with an aliphatic diisocyanate.
12. The cast polyurethane elastomer of claim 11, wherein the mass ratio of polyether polyol to aliphatic diisocyanate is 1:1.5-2.5.
13. The cast polyurethane elastomer of claim 12, wherein the mass ratio of polyether polyol to aliphatic diisocyanate is 1:1.8-2.4.
14. The cast polyurethane elastomer of claim 11, wherein the polyether polyol has a molecular weight of 300 to 4000 and a functionality of 2 to 4;
the aliphatic diisocyanate is selected from any one or a combination of at least two of 1, 6-hexamethylene diisocyanate, 3-isocyanatomethylene-3, 5-trimethylcyclohexyl isocyanate, 4' -dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, 2, 4-and 2, 4-trimethyl-1, 6-hexamethylene diisocyanate mixture and norbornane diisocyanate.
15. The cast polyurethane elastomer of claim 14, wherein the polyether polyol 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.
16. The cast polyurethane elastomer of claim 15, wherein the polyether polyol is selected from any one or a combination of at least two of MN-700, MN-1000, MN-1500.
17. The cast polyurethane elastomer of claim 14, wherein the aliphatic diisocyanate is selected from any one or a combination of at least two of 1, 6-hexamethylene diisocyanate, 4' -dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, 3-isocyanatomethylene-3, 5-trimethylcyclohexyl isocyanate.
18. The cast polyurethane elastomer according to claim 11, wherein the aliphatic isocyanate prepolymer HC-100 is prepared by the following steps: mixing polyether polyol with aliphatic diisocyanate, and reacting at 70-90 ℃ for 3-6 hours.
19. The cast polyurethane elastomer of claim 18, wherein the polyether polyol is reacted with the aliphatic diisocyanate at 75-85 ℃ for 3.5-5 hours.
20. A process for the preparation of a cast polyurethane elastomer as claimed in any one of claims 9 to 19, comprising the steps of: heating and vacuumizing the aliphatic isocyanate prepolymer HC-100, adding the polyurethane chain extender, uniformly mixing, vacuumizing again, pouring into a die which is coated with a release agent in advance, placing into a blast oven at 90-110 ℃ for reacting for 20-50min, and demoulding to obtain the casting polyurethane elastomer.
21. The method for preparing a casting polyurethane elastomer according to claim 20, wherein the aliphatic isocyanate prepolymer HC-100 is heated and vacuumized, the vacuum degree is 50-200Pa, the temperature is 80-130 ℃ and the time is 10-50min;
adding polyurethane chain extender, mixing, and vacuumizing again, wherein the vacuum degree is 50-200Pa, the temperature is 80-130 ℃, and the time is 1-3min;
the reaction is carried out at 100-105 ℃ for 30-40min.
22. The method for preparing a cast polyurethane elastomer according to claim 21, wherein the temperature of the aliphatic isocyanate prepolymer HC-100 is 90-110 ℃ and the time is 20-30min when the temperature is increased and the vacuum is applied.
23. The method for preparing a cast polyurethane elastomer according to claim 21, wherein the temperature is 90-110 ℃ when the polyurethane chain extender is added and mixed and then vacuumized again.
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