CN110964223A

CN110964223A - Application of amine compound with reversible protection of carbon dioxide

Info

Publication number: CN110964223A
Application number: CN201911279741.7A
Authority: CN
Inventors: 杨小牛; 张波; 赵晓礼; 李肖肖; 田雨濛
Original assignee: Changchun Institute of Applied Chemistry of CAS
Current assignee: Changchun Institute of Applied Chemistry of CAS
Priority date: 2019-12-13
Filing date: 2019-12-13
Publication date: 2020-04-07

Abstract

The invention relates to application of an amine compound with carbon dioxide reversible protection, belonging to the technical field of compound application. Solves the technical problem that the polyurethane chemical foaming agent in the prior art can not give consideration to excellent foaming performance and environmental protection. The invention provides an application of a carbon dioxide reversible protective amine compound as a chemical foaming agent for preparing polyurethane foam. The amine compound with carbon dioxide reversible protection has good foaming performance as a chemical foaming agent, can be used as a zero ODP foaming agent for replacing the existing CFCs and HCFCs foaming agents, and can be used for preparing the obtained polyurethane foam material with wide adjustable range of physical and chemical properties and uniform and stable structure.

Description

Application of amine compound with reversible protection of carbon dioxide

Technical Field

The invention relates to application of an amine compound with carbon dioxide reversible protection, belonging to the technical field of compound application.

Background

Different types of polyurethane foams have different excellent properties, such as excellent resilience, low thermal conductivity, excellent compressive strength and tensile strength, and the like, so that the polyurethane foams have a wide range of applications in daily life, and are one of the indispensable materials, particularly in the fields of furniture, bedding, transportation, refrigeration, construction, heat insulation, and the like. The polyurethane soft foam is mainly applied to furniture, bedding and other household articles, such as sofas, seats, backrest cushions, mattresses and pillows; the polyurethane hard foam is mainly used for heat insulation and preservation, refrigeration and freezing equipment and a cold storage, heat insulation plates, wall heat insulation, pipeline heat insulation, heat insulation of a storage tank, single-component foam joint filling materials and the like. However, the physical blowing agents, chlorofluorocarbons (CFCs), which have long been used to produce rigid polyurethane foams, have a severe damaging effect on the atmospheric ozone layer and therefore have severe limitations in their use and production. With the increasing importance of environmental protection in countries around the world, developed countries have stopped using second generation physical blowing agents in 2003, and developing countries have also promised to stop using physical blowing agents that are hazardous to the atmospheric ozone layer in 2030 to prepare polyurethane foams.

Disclosure of Invention

The invention aims to solve the technical problem that the polyurethane chemical foaming agent in the prior art cannot give consideration to excellent foaming performance and environmental protection.

The technical scheme adopted by the invention for solving the technical problems is as follows.

The amine compound reversibly protected by carbon dioxide is applied as a chemical foaming agent for preparing a polyurethane foam material;

the structural formula of the amine compound reversibly protected by carbon dioxide is one of formula I, formula II, formula III, formula IV and formula V:

in the formula I, the formula II, the formula III and the formula IV, n, m, p and q are integers, n is more than or equal to 1 and less than or equal to 20, m is more than or equal to 1 and less than or equal to 10, and p is more than or equal to 1 and less than or equal to 10Q is more than or equal to 20 and 1 and less than or equal to 20, and R is CH₂Or CH₂CH₂，R₁Is CH₂CH(CH₃) Or CH₂CH₂。

Preferably, n is more than or equal to 2 and less than or equal to 15, m is more than or equal to 1 and less than or equal to 5, p is more than or equal to 1 and less than or equal to 10, and q is more than or equal to 1 and less than or equal to 10; more preferably, 2. ltoreq. n.ltoreq.10, 1. ltoreq. m.ltoreq.3, 1. ltoreq. p.ltoreq.5, 1. ltoreq. q.ltoreq.5.

Preferably, the amine compound with carbon dioxide reversible protection is added into the polyurethane prepolymer with NCO content of 3% -9%, the mixture is uniformly mixed, then the foam stabilizer is added and uniformly mixed, the micromolecule diol chain extender is added and uniformly mixed, finally the catalyst is added and uniformly mixed, the obtained mixture is transferred into a mold with the temperature of 80-200 ℃, and the polyurethane foam material is obtained through free foaming.

More preferably, the stirring speed for uniform mixing is 1000-5000rpm, the mixing time of the amine compound reversibly protected by carbon dioxide and the polyurethane prepolymer is 5-30min, the mixing time of adding the foam stabilizer is 1-10min, the mixing time of adding the small molecular glycol chain extender is 1-5min, and the mixing time of adding the catalyst is 1-5 min.

More preferably, the mass ratio of the amine compound reversibly protected by carbon dioxide to the polyurethane prepolymer is (2.925-7.822): 200.

More preferably, the foam stabilizer is B8 or L64, and the mass ratio of the foam stabilizer to the polyurethane prepolymer is (6-10): 200.

More preferably, the small molecular glycol chain extender is 1,4 butanediol, and the mass ratio of the small molecular glycol chain extender to the polyurethane prepolymer is (4.671-8.41): 200.

More preferably, the catalyst is DB40, triethylamine or dibutyltin dilaurate, and the mass ratio of the catalyst to the polyurethane prepolymer is (0.2-0.6): 200.

The principle of the invention is as follows: the amine compound reversibly protected by carbon dioxide is decomposed by carboxylate under the heating condition to release carbon dioxide and amine (monoamine, diamine or polyamine), wherein the carbon dioxide can play a foaming role, and the released amine participates in chain extension reaction.

Compared with the prior art, the invention has the beneficial effects that:

the amine compound with reversible protection of carbon dioxide as a chemical foaming agent has good foaming performance, can be used as a zero ODP foaming agent for replacing the existing CFCs and HCFCs foaming agents, has good compatibility with polyurethane systems (polyurethane white materials, polyurethane prepolymers and the like), is stable and not easy to volatilize at room temperature, and can decompose and release carbon dioxide and amine only by the decomposition of carboxylate under the heating condition, so that the foaming operation time is adjustable, and the prepared polyurethane foaming material has a large adjustable range of volume; the released carbon dioxide is used for polyurethane foaming, and in addition, the released amine can react with a plurality of isocyanates, so that the strength of the foam material is improved, and the physical and chemical properties of the prepared polyurethane foam material have a wide adjustable range; in addition, the amine compound with carbon dioxide reversible protection has good dispersibility in a polyurethane system as a chemical foaming agent, and gas is more uniformly dispersed in materials in the foaming process, so that the cell size is improved, the obtained polyurethane foam has uniform and stable structure, and the foaming efficiency is higher compared with that of water as the chemical foaming agent.

Drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a graph showing the front and rear loop curves before and after fatigue of a polyurethane foam of example 3 of the present invention;

FIG. 2 is a graph showing the front and rear loop curves before and after fatigue of the polyurethane foam of example 5 of the present invention;

FIG. 3 is a graph showing the front and rear loop curves of polyurethane foam of example 7 according to the present invention before and after fatigue;

FIG. 4 is a graph showing the front and rear loop curves before and after fatigue of the polyurethane foam of example 10 of the present invention;

FIG. 5 is a graph showing the front and rear loop curves of polyurethane foam of example 14 of the present invention before and after fatigue;

FIG. 6 is a graph showing the front and rear loop curves before and after fatigue of the polyurethane foam of example 16 of the present invention;

FIG. 7 is a graph showing the front and rear loop curves of polyurethane foam of example 20 of the present invention before and after fatigue.

Detailed Description

In order that the invention may be more clearly understood, the invention has been described in further detail with reference to specific embodiments. It should be understood that the embodiments described herein are illustrative only and are not limiting upon the claims of the present invention.

The invention provides application of amine compounds reversibly protected by carbon dioxide as a chemical foaming agent for preparing polyurethane foam materials;

formula I, formula II, formula III and formula IV, n, m, p and q are integers; n is 1. ltoreq. n.ltoreq.20, preferably 2. ltoreq. n.ltoreq.15, more preferably 2. ltoreq. n.ltoreq.10; 1. ltoreq. m.ltoreq.10, preferably 1. ltoreq. m.ltoreq.5, more preferably 1. ltoreq. m.ltoreq.3; 1. ltoreq. p.ltoreq.20, preferably 1. ltoreq. p.ltoreq.10, more preferably 1. ltoreq. p.ltoreq.5; 1. ltoreq. q.ltoreq.20, preferably 1. ltoreq. q.ltoreq.10, more preferably 1. ltoreq. q.ltoreq.5; r is CH₂Or CH₂CH₂；R₁Is CH₂CH(CH₃) Or CH₂CH₂。

In the above technical scheme, the amine compound reversibly protected by carbon dioxide is the prior art, and the invention provides a preparation method thereof, but is not limited thereto: dissolving aliphatic unit amine, diamine or aliphatic triamine in an organic solvent, stirring and reacting at 100-400rpm for 5-60min in a carbon dioxide atmosphere with the gas flow of 1-20ml/min at the temperature of 0-25 ℃, and filtering, cleaning and drying after the reaction is finished to obtain the amine compound with reversible protection of carbon dioxide.

In the method for producing the amine compound reversibly protected with carbon dioxide, the organic solvent is not particularly limited, and may be used as long as it can dissolve the corresponding raw material, and Tetrahydrofuran (THF) is preferable. The aliphatic amine unit can be ethylamine or hexylamine. The aliphatic diamine can be aliphatic alkane diamine such as ethylenediamine, 1, 6-diamine hexane, 1, 10-diamine decane; can be aliphatic ether diamine 2,2' -oxybis (ethylamine), 2' - [1, 2-ethanediyl (oxy) ] bis-ethylamine, 2' - [ oxybis (2, 1-ethanediyloxy) ] bis-ethylamine, 1- (2-aminoethoxy) propane-2-amine; it may be an aliphatic ester diamine such as 1-amino-2-propanol carbamate. The aliphatic triamine is aliphatic alkane triamine, such as N, N-bis (aminomethyl) -methane diamine, N-bis (2-aminoethyl) -1, 2-ethanediamine, and N, N-bis (4-aminobutyl) -1, 4-butanediamine. The reaction temperature and time are preferably varied depending on the aliphatic polyamine: when the aliphatic polyamine is aliphatic alkane diamine, the stirring speed is preferably 100-300rpm, and the reaction is carried out for 5-30 min; when the aliphatic polyamine is aliphatic ether diamine, aliphatic ester diamine or aliphatic triamine, the stirring speed is preferably 100-400rpm, and the reaction is carried out for 20-60 min; when the aliphatic polyamine is aliphatic triamine or aliphatic diamine with less than six carbon atoms, the reaction temperature is preferably 0-10 ℃, and the temperature can be obtained by adopting an ice-water bath reaction. Diethyl ether is generally used as the cleaning agent.

In the technical scheme, the application of the amine compound reversibly protected by carbon dioxide as a chemical foaming agent for preparing the polyurethane foam material comprises the following steps: adding an amine compound with carbon dioxide reversible protection into a polyurethane prepolymer with NCO content of 3% -9%, uniformly mixing, then adding a foam homogenizing agent, uniformly mixing, then adding a small-molecular-weight glycol chain extender, uniformly mixing, finally adding a catalyst, uniformly mixing, transferring the obtained mixture into a mold at 80-200 ℃, and freely foaming to obtain the polyurethane foam material.

In the application, the mass ratio of the amine compound reversibly protected by carbon dioxide to the polyurethane prepolymer is (2.925-7.822): 200.

In the above application, the foam stabilizer is a small molecule or a low molecular weight polymer capable of reducing the surface tension of the prepolymer mixture, and the foam stabilizer of the present invention is preferably foam stabilizer B8 or foam stabilizer L64, but is not limited to the foam stabilizer used in the embodiment of the present invention; the mass ratio of the foam stabilizer to the polyurethane prepolymer is (6-10): 200. The small molecule diol chain extender can be a diol chain extender commonly used in polyurethane systems, preferably 1, 4-butanediol, but is not limited thereto; the mass ratio of the micromolecular diol chain extender to the polyurethane prepolymer is (4.671-8.41): 200. The catalyst can be amine or metallic tin catalyst capable of catalyzing polyurethane gel reaction rate, preferably triethylamine, DB40, dibutyltin dilaurate, but is not limited to the above; the mass ratio of the catalyst to the polyurethane prepolymer is (0.2-0.6): 200.

In the application, the stirring speed for uniform mixing is 1000-5000rpm, the mixing time of the amine compound reversibly protected by carbon dioxide and the polyurethane prepolymer is 5-30min, the mixing time of adding the foam stabilizer is 1-10min, the mixing time of adding the small molecular glycol chain extender is 1-5min, and the mixing time of adding the catalyst is 1-5 min.

The polyurethane prepolymer with NCO content of 3% -9% of the invention is the prior art, the invention provides a preparation method thereof, but is not limited to the following steps: adding oligomeric polyol into a reaction container, dehydrating at 130 ℃ under the vacuum degree of 50-500Pa, adding diisocyanate under the protection of inert atmosphere, and heating at 70-130 ℃ for reaction to obtain the polyurethane prepolymer with the required NCO content of 3% -9%.

In the preparation method of the polyurethane prepolymer, the NCO content of the polyurethane prepolymer is detected by a di-n-butylamine method; weighing a prepolymer with the mass of m (about 0.5g), putting the prepolymer into a 250ml conical flask, adding 25ml of anhydrous toluene, covering a bottle stopper, oscillating to completely dissolve a sample, sucking 20ml of a di-n-butylamine anhydrous toluene solution into the conical flask by using a pipette, covering the bottle stopper, oscillating for about 15min, adding 100ml of isopropanol, dripping 4-6 drops of a bromocresol blue indicator, titrating by using a hydrochloric acid standard solution (with the concentration of C1) until the solution turns yellow from blue to consume a hydrochloric acid volume V2, calibrating a hydrochloric acid volume V1 consumed by blank di-n-butylamine, and calculating the NCO content according to the following formula;

NCO％＝(V1-V2)*C1×4.2/m。

the oligomeric polyol is one or more of polyester polyol, polyether polyol, polycarbonate polyol and polymer polyol. Preferably polytetrahydrofuran Polyol (PTMG), the degree of polymerization n is 11-33; polypropylene oxide polyol (PPO) with a degree of polymerization m of 13-39; polycarbonate Polyol (PCDL), the degree of polymerization is 4-17, and R is tetramethylene, pentamethylene or hexamethylene; poly-epsilon-caprolactone Polyol (PCL), the polymerization degree Q is 7-22; the structural formulas are respectively as follows:

the oligomeric polyols used include, but are not limited to, the foregoing.

The isocyanate is one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1, 5-Naphthalene Diisocyanate (NDI), p-phenylene diisocyanate (PPDI) and isophorone diisocyanate (IPDI); the structural formulas are respectively as follows:

the present invention is further illustrated by the following examples.

Example 1

The application of the amine compound reversibly protected by carbon dioxide as a chemical foaming agent for preparing the polyurethane foam material comprises the following steps:

step one, adding 1000g of PPO (molecular weight 1000) into a three-neck flask, dehydrating for 2h under the vacuum degree of 300pa and 130p, cooling to 70 ℃, adding 500.52g of MDI under the protection of nitrogen, reacting for 1.5h to obtain a polyurethane prepolymer, and titrating to obtain the NCO content of the polyurethane prepolymer of 5.6%.

Step two, 4.176g of amine compound with carbon dioxide reversible protection and 200g of polyurethane prepolymer are uniformly mixed, stirred for 10min at the rotating speed of 1500rpm, then 8g B8 foam stabilizer is added, stirred for 3min, 8.41g of 1, 4-butanediol is added, stirred for 3min, and finally catalyst DB400.6g is added and stirred for 1 min;

the structure of the amine compound reversibly protected by carbon dioxide is as follows:

and step three, transferring the mixture obtained in the step two into a mold at 150 ℃ for free foaming to obtain the polyurethane foam material.

Example 2

step one, adding 2000g of PCDL (molecular weight 2000) into a three-neck flask, heating to 130 ℃, dehydrating for 2h under-0.98 MPa, cooling to 70 ℃, adding 500.52g of MDI under the protection of nitrogen, reacting for 1.5h to obtain a polyurethane prepolymer, and titrating to obtain the polyurethane prepolymer with NCO content of 3.36%.

Uniformly mixing 3.845g of amine compound reversibly protected by carbon dioxide and 200g of polyurethane prepolymer, stirring at 2000rpm for 10min, adding 8g B8 foam stabilizer, stirring for 3min, adding 5.047g of 1, 4-butanediol, stirring for 3min, and finally adding DB400.4g of catalyst, and stirring for 1 min;

and step three, transferring the mixture obtained in the step two into a 140 ℃ mold, and freely foaming to obtain the polyurethane foam material.

Example 3

step one, adding 1000g PTMG (molecular weight 1000) into a three-neck flask, heating to 130 ℃, dehydrating for 2h under-0.98 MPa, cooling to 90 ℃, adding 348.32g TDI80 under the protection of nitrogen, reacting for 4h to obtain a polyurethane prepolymer, and titrating to obtain the polyurethane prepolymer with NCO content of 3.11%.

Step two, 2.977g of amine compound with carbon dioxide reversible protection and 200g of polyurethane prepolymer are uniformly mixed, stirred for 9min at the rotating speed of 1000rpm, then 7g B8 foam stabilizer is added, stirred for 3min, 4.671g of 1,4 butanediol is added, stirred for 2min, finally catalyst DB400.4g is added, and stirred for 1.5 min.

Example 4

step one, adding 2000g of PCL (molecular weight 2000) into a three-neck flask, heating to 130 ℃, dehydrating for 2h under the vacuum degree of 400pa, cooling to 70 ℃ under the protection of nitrogen, adding 320.26g of PPDI, reacting for 1.5h to obtain a polyurethane prepolymer, and titrating to obtain the NCO content of 3.66%.

Step two, 2.977g of amine compound with carbon dioxide reversible protection and 200g of polyurethane prepolymer are uniformly mixed, stirred for 9min at the rotating speed of 1000rpm, then 7g B8 foam stabilizer is added, stirred for 3min, 4.671g of 1,4 butanediol is added, stirred for 1.5min, and finally catalyst DB400.4g is added and stirred for 1 min;

Example 5

step one, adding 2000g of PCDL (molecular weight 2000) into a three-neck flask, heating to 130 ℃, dehydrating for 2h under the vacuum degree of 300pa, cooling to 70 ℃ under the protection of nitrogen, adding 320.26g of PPDI, reacting for 1.5h to obtain a polyurethane prepolymer, and titrating to obtain the NCO content of 3.62%.

Step two, 4.862g of amine compound with carbon dioxide reversible protection and 200g of polyurethane prepolymer are uniformly mixed, stirred for 11min at the rotating speed of 1000rpm, then 7g L64 foam stabilizer is added, stirred for 3min, 5.436g of 1,4 butanediol is added, stirred for 1.5min, and finally catalyst DB400.4g is added and stirred for 1 min;

and step three, transferring the mixture obtained in the step two into a 160 ℃ mold, and freely foaming to obtain the polyurethane foam material.

Example 6

step one, adding 2000g PPG (molecular weight 2000) into a three-neck flask, heating to 130 ℃, dehydrating for 2h under the vacuum degree of 300pa, cooling to 70 ℃ under the protection of nitrogen, adding 320.26g PPDI, reacting for 1.5h to obtain a polyurethane prepolymer, and titrating to obtain the NCO content of 3.62%.

Step two, 7.822g of amine compound with carbon dioxide reversible protection and 200g of polyurethane prepolymer are uniformly mixed, stirred at the rotation speed of 1800rpm for 10min, then 10g L64 foam stabilizer is added, stirred for 3min, 5.436g of 1,4 butanediol is added, stirred for 3min, and finally catalyst DB400.4g is added, and stirred for 1 min;

Example 7

step one, adding 2000g PTMG (molecular weight 2000) into a three-neck flask, heating to 130 ℃, dehydrating for 2h under the vacuum degree of 300pa, cooling to 70 ℃, adding 420.38g NDI under the protection of nitrogen, reacting for 1.5h to obtain a polyurethane prepolymer, and titrating to obtain the NCO content of 3.47%.

Step two, 3.668g of amine compound with carbon dioxide reversible protection and 200g of polyurethane prepolymer are uniformly mixed, stirred at the rotation speed of 1800rpm for 10min, then 10g B8 foam stabilizer is added, stirred for 3min, 5.212g of 1, 4-butanediol is added, stirred for 3min, and finally catalyst triethylamine is added, 0.2g of triethylamine is added, and stirred for 1 min;

and step three, transferring the mixture obtained in the step two into a 130 ℃ mold, and freely foaming to obtain the polyurethane foam material.

Example 8

step one, adding 2000g of PCL (molecular weight 2000) into a three-neck flask, heating to 130 ℃, dehydrating for 2h under the vacuum degree of 300pa, cooling to 70 ℃ under the protection of nitrogen, adding 420.38g of NDI, reacting for 1.5h to obtain a polyurethane prepolymer, and titrating to obtain the NCO content of 3.47%.

Step two, 4.764g of amine compound with carbon dioxide reversible protection and 200g of polyurethane prepolymer are uniformly mixed, stirred for 9min at the rotating speed of 2500rpm, then 8g B8 foam stabilizer is added, stirred for 5min, 5.212g of 1, 4-butanediol is added, stirred for 3min, and finally catalyst triethylamine is added, 0.2g of triethylamine is added, and stirred for 0.5 min;

Example 9

step one, adding 2000g of PPO (molecular weight 2000) into a three-neck flask, heating to 130 ℃, dehydrating for 2h under the vacuum degree of 300pa, cooling to 70 ℃ under the protection of nitrogen, adding 420.38g of NDI, reacting for 1.5h to obtain a polyurethane prepolymer, and titrating to obtain the NCO content of 3.47%.

Step two, 5.852g of amine compound with carbon dioxide reversible protection and 200g of polyurethane prepolymer are uniformly mixed, stirred for 10min at the rotating speed of 2000rpm, then 8g B8 foam stabilizer is added, stirred for 4min, 5.212g of 1, 4-butanediol is added, stirred for 2min, and finally catalyst triethylamine is added, 0.4g of triethylamine is added, and stirred for 1 min.

and step three, transferring the mixture obtained in the step two into a 100 ℃ mold, and freely foaming to obtain the polyurethane foam material.

Example 10

step one, adding 2000g of PPO (molecular weight 2000) into a three-neck flask, heating to 130 ℃, dehydrating for 2h under the vacuum degree of 300pa, cooling to 70 ℃, adding 444.48g of IPDI under the protection of nitrogen, reacting for 1.5h to obtain a polyurethane prepolymer, and titrating to obtain the NCO content of 3.44%.

And step two, uniformly mixing 3.985g of amine compound reversibly protected by carbon dioxide and 200g of polyurethane prepolymer, stirring at the rotating speed of 2000rpm for 8min, adding 6g B8 foam stabilizer, stirring for 5min, adding 5.167g of 1, 4-butanediol, stirring for 2min, adding 0.4g of catalyst dibutyltin dilaurate, and stirring for 1 min.

Example 11

step one, adding 2000g of PCDL (molecular weight 2000) into a three-neck flask, heating to 130 ℃, dehydrating for 2h under the vacuum degree of 300pa, cooling to 70 ℃ under the protection of nitrogen, adding 444.48g of IPDI, reacting for 1.5h to obtain a polyurethane prepolymer, and titrating to obtain the NCO content of 3.44%.

And step two, uniformly mixing 3.985g of amine compound reversibly protected by carbon dioxide and 200g of polyurethane prepolymer, stirring at the rotating speed of 1600rpm for 10min, adding 8g B8 foam stabilizer, stirring for 3min, adding 5.167g of 1, 4-butanediol, stirring for 2min, adding 0.4g of catalyst dibutyltin dilaurate, and stirring for 1 min.

Example 12

step one, adding 2000g PTMG (molecular weight 2000) into a three-neck flask, heating to 130 ℃, dehydrating for 2h under the vacuum degree of 300pa, cooling to 70 ℃, adding 500.52g MDI under the protection of nitrogen, reacting for 1.5h to obtain a polyurethane prepolymer, and titrating to obtain the NCO content of 3.34%.

And step two, uniformly mixing 3.15g of amine compound reversibly protected by carbon dioxide and 200g of polyurethane prepolymer, stirring at the rotating speed of 1200rpm for 10min, adding 10g B8 foam stabilizer, stirring for 3min, adding 5.017g of 1, 4-butanediol, stirring for 2min, adding 0.2g of dibutyltin dilaurate serving as a catalyst, and stirring for 1 min.

Example 13

step one, adding 2000g PTMG (molecular weight 2000) into a three-neck flask, heating to 130 ℃, dehydrating for 2h under the vacuum degree of 300pa, cooling to 70 ℃, adding 320.26g PPDI under the protection of nitrogen, reacting for 1.5h to obtain a polyurethane prepolymer, and titrating to obtain the NCO content of 3.6%.

Step two, 3.977g of amine compound with carbon dioxide reversible protection and 200g of polyurethane prepolymer are uniformly mixed, stirred at the rotating speed of 1200rpm for 10min, then 10g B8 foam stabilizer is added, stirred for 3min, 5.407g of 1, 4-butanediol is added, stirred for 2min, and finally, 0.2g of dibutyltin dilaurate serving as a catalyst is added, and stirred for 1 min.

and step three, transferring the mixture obtained in the step two into a 170 ℃ mold, and freely foaming to obtain the polyurethane foam material.

Example 14

step one, adding 2000g of PCL (molecular weight 2000) into a three-neck flask, heating to 130 ℃, dehydrating for 2h under the vacuum degree of 300pa, cooling to 70 ℃ under the protection of nitrogen, adding 444.48g of IPDI, reacting for 1.5h to obtain a polyurethane prepolymer, and titrating to obtain the NCO content of 3.44%.

Step two, 5.183g of amine compound with carbon dioxide reversible protection and 200g of polyurethane prepolymer are uniformly mixed, stirred at the rotation speed of 1800rpm for 10min, then 8g B8 foam stabilizer is added, stirred for 2.5min, 5.167g of 1, 4-butanediol is added, stirred for 2min, and finally, catalyst dibutyltin dilaurate is added, and stirred for 1min, wherein the catalyst dibutyltin dilaurate is 0.4 g.

Example 15

step one, adding 2000g of PPO (molecular weight 2000) into a three-neck flask, heating to 130 ℃ and carrying out

Dehydrating for 2h under the vacuum degree of 300pa, cooling to 70 ℃ under the protection of nitrogen, adding 420.38g of NDI, reacting for 1.5h to obtain a polyurethane prepolymer, and titrating to obtain the NCO content of 3.47%.

Step two, 2.925g of amine compound with carbon dioxide reversible protection and 200g of polyurethane prepolymer are uniformly mixed, stirred for 10min at the rotating speed of 2000rpm, then 8g B8 foam stabilizer is added, stirred for 4min, 5.212g of 1, 4-butanediol is added, stirred for 3min, and finally catalyst triethylamine is added, 0.4g of triethylamine is added, and stirred for 1 min.

and step three, transferring the mixture obtained in the step two into a 190 ℃ mold, and freely foaming to obtain the polyurethane foam material.

Example 16

step one, adding 2000g of PCDL (molecular weight 2000) into a three-neck flask, heating to 130 ℃, dehydrating for 2h under the vacuum degree of 300pa, cooling to 70 ℃ under the protection of nitrogen, adding 420.38g of NDI, reacting for 1.5h to obtain a polyurethane prepolymer, and titrating to obtain the NCO content of 3.47%.

Step two, 3.272g of amine compound with carbon dioxide reversible protection and 200g of polyurethane prepolymer are uniformly mixed, stirred for 10min at the rotating speed of 3000rpm, then 8g B8 foam stabilizer is added, stirred for 4min, 5.212g of 1, 4-butanediol is added, stirred for 3min, and finally catalyst triethylamine is added, 0.3g of triethylamine is added, and stirred for 1 min.

and step three, transferring the mixture obtained in the step two into a 180 ℃ mold, and freely foaming to obtain the polyurethane foam material. .

Example 17

step one, adding 2000g PCL (molecular weight 2000) into a three-neck flask, heating to 130 ℃ and cooling

Dehydrating for 2h under the vacuum degree of 300pa, cooling to 70 ℃ under the protection of nitrogen, adding 348.32g of TDI, reacting for 1.5h to obtain a polyurethane prepolymer, and titrating to obtain the NCO content of 3.58%.

Step two, 3.738g of amine compound with carbon dioxide reversible protection and 200g of polyurethane prepolymer are uniformly mixed, stirred at the rotating speed of 2500rpm for 10min, then 8g B8 foam stabilizer is added, stirred for 5min, 5.377g of 1, 4-butanediol is added, stirred for 4min, and finally catalyst triethylamine 0.6g is added, and stirred for 2 min.

Example 18

step one, adding 2000g of PPO (molecular weight 2000) into a three-neck flask, heating to 130 ℃, dehydrating for 2h under the vacuum degree of 300pa, cooling to 70 ℃ under the protection of nitrogen, adding 348.32g of TDI, reacting for 1.5h to obtain a polyurethane prepolymer, and titrating to obtain the NCO content of 3.58%.

Step two, 4.455g of amine compound with carbon dioxide reversible protection and 200g of polyurethane prepolymer are uniformly mixed, stirred for 10min at the rotating speed of 2500rpm, then 8g B8 foam stabilizer is added, stirred for 5min, 5.377g of 1, 4-butanediol is added, stirred for 4min, and finally catalyst triethylamine 0.6g is added, and stirred for 2 min.

Example 19

Step two, 5.294g of amine compound with carbon dioxide reversible protection and 200g of polyurethane prepolymer are uniformly mixed, stirred for 10min at the rotating speed of 3000rpm, then 8g B8 foam stabilizer is added, stirred for 5min, 4.467g of 1, 4-butanediol is added, stirred for 5min, and finally catalyst triethylamine is added, 0.4g of triethylamine is added, and stirred for 1 min.

Example 20

Step two, 3.971g of amine compound with carbon dioxide reversible protection and 200g of polyurethane prepolymer are uniformly mixed, stirred for 10min at the rotating speed of 2500rpm, then 8g B8 foam stabilizer is added, stirred for 5min, 5.212g of 1, 4-butanediol is added, stirred for 4min, and finally catalyst triethylamine 0.4g is added, and stirred for 2 min.

The polyurethane foams obtained in examples 1 to 20 were subjected to the following tests:

1. and (5) testing mechanical properties. The test method comprises the following steps: (1) cutting 5 identical samples of polyurethane foam according to national standard GB/T10807-2006, and measuring the length, width and thickness of each sample before stretching; (2) the compression was performed using an INSTRON5982 model electronic tester with a compression rate of 20mm/min and a preload force of 1 Newton, and the compressive strength of 40% compression for each sample was calculated. Each sample was subjected to a pre-compaction test prior to compression, the pre-compaction was repeated 20% at least 3 times, and the test results are shown in table 1.

2. And (5) testing the density. The test method comprises the following steps: according to the national standard GB/T6343-95, at least 3 samples are prepared for each sample, the weight of the samples is accurately weighed on an analytical balance to 0.01g, and the size of the samples is measured by a micrometer caliper. To the nearest 0.1 mm. The average was taken in triplicate for each sample. The results are shown in Table 1

TABLE 1 mechanical Property test results for polyurethane foams of examples 1-10

From examples 1 to 20, it can be seen that the amine compound reversibly protected by carbon dioxide can realize the preparation of the polyurethane foam material in a common polyurethane system, and the prepared polyurethane foam material has good mechanical properties.

The materials prepared in some of the examples were subjected to a compression fatigue performance study using a fatigue tester under the following test conditions: the pre-compression before compression was 50%, the amplitude was 2mm, the frequency was 5Hz, and the number of fatigue cycles was 100000, and the compression loop curves before and after the fatigue test of polyurethane foam were compared, the material of the fatigue test was from examples 3, 5, 7, 10, 14, 16, and 20, and the results are shown in FIGS. 1 to 7.

From fatigue tests, the polyurethane foam prepared by the amine compound reversibly protected by the carbon dioxide has good fatigue resistance, the loop curves before and after the fatigue test are basically superposed, and the foam material basically has no permanent deformation after the fatigue test is finished.

It is obvious that the above description of embodiments is only intended to facilitate the understanding of the method and the core idea of the invention. It should be noted that it is possible for a person skilled in the art to make several improvements and modifications to the present invention without departing from the precursors of the inventive method, such as adjusting the properties of polyurethane foams by using different amounts of amine compounds reversibly protected with carbon dioxide; prepolymers with different NCO contents are obtained by changing the mixture ratio of raw materials; different catalysts and foam homogenizing agents are adopted, and the purpose of optimizing the performance of the polyurethane foam is achieved by optimizing the using amount of the foam homogenizing agents; such improvements and modifications are intended to fall within the scope of the appended claims.

Claims

1. The application of amine compounds reversibly protected by carbon dioxide as chemical foaming agents for preparing polyurethane foam materials;

in the formula I, the formula II, the formula III and the formula IV, n, m, p and q are integers, n is more than or equal to 1 and less than or equal to 20, m is more than or equal to 1 and less than or equal to 10, p is more than or equal to 1 and less than or equal to 20, q is more than or equal to 1 and less than or equal to 20, R is CH₂Or CH₂CH₂，R₁Is CH₂CH(CH₃) Or CH₂CH₂。

2. The use of amine compounds reversibly protected by carbon dioxide as blowing agents for the preparation of polyurethane foams according to claim 1, characterized in that 2. ltoreq. n.ltoreq.15, 1. ltoreq. m.ltoreq.5, 1. ltoreq. p.ltoreq.10, 1. ltoreq. q.ltoreq.10.

3. The use of amine compounds reversibly protected with carbon dioxide as blowing agents for the preparation of polyurethane foams according to claim 2, characterized in that 2. ltoreq. n.ltoreq.10, 1. ltoreq. m.ltoreq.3, 1. ltoreq. p.ltoreq.5, 1. ltoreq. q.ltoreq.5.

4. The application of the amine compound reversibly protected by carbon dioxide as the chemical foaming agent for preparing the polyurethane foam material according to any one of claims 1 to 3 is characterized in that the amine compound reversibly protected by carbon dioxide is added into the polyurethane prepolymer with NCO content of 3-9%, the mixture is uniformly mixed, then the foam homogenizing agent is added and uniformly mixed, then the micromolecule diol chain extender is added and uniformly mixed, finally the catalyst is added and uniformly mixed, the obtained mixture is transferred into a mold with the temperature of 80-200 ℃, and the polyurethane foam material is obtained by free foaming.

5. The application of the amine compound reversibly protected by carbon dioxide as the chemical foaming agent for preparing the polyurethane foam material as claimed in claim 4, wherein the stirring speed for uniform mixing is 1000-5000rpm, the mixing time of the amine compound reversibly protected by carbon dioxide and the polyurethane prepolymer is 5-30min, the mixing time of adding the foam stabilizer is 1-10min, the mixing time of adding the small molecular glycol chain extender is 1-5min, and the mixing time of adding the catalyst is 1-5 min.

6. The application of the amine compound reversibly protected by carbon dioxide as the chemical foaming agent for preparing the polyurethane foam material according to claim 4, wherein the mass ratio of the amine compound reversibly protected by carbon dioxide to the polyurethane prepolymer is (2.925-7.822): 200.

7. The use of the amine compound reversibly protected by carbon dioxide as a chemical blowing agent for preparing polyurethane foam material according to claim 4, wherein the foam stabilizer is B8 or L64, and the mass ratio of the foam stabilizer to the polyurethane prepolymer is (6-10): 200.

8. The application of the amine compound reversibly protected by carbon dioxide as the chemical foaming agent for preparing the polyurethane foam material is characterized in that the micromolecular diol chain extender is 1,4 butanediol, and the mass ratio of the micromolecular diol chain extender to the polyurethane prepolymer is (4.671-8.41): 200.

9. The use of the amine compound reversibly protected by carbon dioxide as a chemical blowing agent for preparing polyurethane foam according to claim 4, wherein the catalyst is DB40, triethylamine or dibutyltin dilaurate, and the mass ratio of the catalyst to the polyurethane prepolymer is (0.2-0.6): 200.