CN117866164B

CN117866164B - Metal oxide composite catalytic material and preparation method and application thereof

Info

Publication number: CN117866164B
Application number: CN202410049151.XA
Authority: CN
Inventors: 郁天宇; 蔡新华; 王明轩
Original assignee: Shanghai Yueda Energy Saving Technology Co ltd
Current assignee: Shanghai Yueda Energy Saving Technology Co ltd
Priority date: 2024-01-12
Filing date: 2024-01-12
Publication date: 2024-08-30
Anticipated expiration: 2044-01-12
Also published as: CN117866164A

Abstract

The invention relates to the technical field of catalysts and polyurethane hard foam materials, in particular to a metal oxide composite catalytic material, a preparation method and application thereof, wherein the metal oxide composite catalytic material comprises a carrier and an active ingredient loaded on the carrier; the carrier is any one of alumina, zirconia, silica, activated carbon and graphite. According to the invention, the inert material is used as a carrier, the metal oxide is dispersed on the surface of the inert material to obtain the solid catalyst, and the solid catalyst is used for preparing the polyurethane hard foam by replacing a liquid catalyst commonly used in the market, so that the catalytic effect can be improved, the compressive strength and the high-low temperature dimensional stability of the polyurethane hard foam material can be improved, the cost is greatly reduced, and the problems of high irritation, high toxicity, easiness in hydrolysis failure, relatively poor catalytic effect and the like of the catalyst for spraying the polyurethane hard foam are solved.

Description

Metal oxide composite catalytic material and preparation method and application thereof

Technical Field

The invention relates to the technical field of catalysts and polyurethane hard foam materials, in particular to a metal oxide composite catalytic material, a preparation method and application thereof.

Background

The spray-type polyurethane hard foam material is a waterproof heat-insulating material formed by mixing polyurethane combined polyether and polymeric isocyanate, atomizing the polyurethane combined polyether and the polymeric isocyanate by high-pressure gas under the conveying of a pump, and then spraying the mixture on the surface of a building and automatically expanding. It is a highly closed-cell material, has excellent heat insulation performance, the heat conductivity coefficient is less than or equal to 0.024W/(m is K), the waterproof performance is very good, and simultaneously, the waterproof adhesive can be firmly adhered to the surface of a cement layer or a waterproof layer. The spray-type polyurethane hard foam can be constructed on site, the construction efficiency is very high, two constructors can spray over 40m ³ of heat insulation materials (800-1000 m ² of a cold storage and 1500-3000m ² of an outer wall) each day, and the speed is over 3 times of that of a hanging plate process. And the density of the transported liquid raw material is 1100kg/m ³, compared with the transported polyurethane hard foam insulation board (the density is 45kg/m ³), the transportation cost is greatly saved. Therefore, the polyurethane hard foam thermal insulation material is always the thermal insulation material most commonly used for a cold storage, a fresh-keeping storage and a building roof.

However, the spray-type polyurethane hard foam material is subjected to field construction spraying, so that in order to improve the spraying efficiency, the combined polyether and the polymeric isocyanate are required to be mixed uniformly rapidly, then the mixture is sprayed on the surface of a wall body, the reaction is started within 3 seconds, the foaming is finished within 10 seconds, the mixture has certain strength and cannot flow, 30% of the total strength is achieved within 30 seconds, and the total strength is 60% of 120 seconds. In summary, the raw material polyether composition for spray polyurethane rigid foam must contain a large amount of various catalysts such as organic amine (ammonium) catalyst, potassium catalyst, organotin catalyst, etc., and since the polyether composition is a weakly polar organic liquid, the catalyst must be liquid or be soluble in the weakly polar organic liquid, which greatly limits the range of options for the polyether composition. It is worth emphasizing that most of the spray polyurethane hard foam catalysts at present have strong toxicity, such as the most commonly used pentamethyldiethylenetriamine (PC 5), have strong ammonia-stimulated taste, and a small amount of contact can cause redness and swelling of the cornea of eyes; stannous octoate catalyst (T12), organotin is a highly toxic material and is susceptible to hydrolytic failure; less harmful potassium ion and alcohol amine catalysts, such as potassium acetate and triethanolamine, have general catalytic effects, and have little effect especially on early-stage inspired expansion foaming.

Therefore, there is a strong need for a high cost performance, safe, non-toxic, long-life catalyst or series of catalysts that can be well dissolved in the combined polyether. In addition, the use of the foaming agent 141b commonly used at present is totally forbidden in 2025, water is used as a chemical foaming agent instead of 141b in the combined polyether, the use amount of the all-water spraying polyurethane hard foam is gradually increased, even the all-water spraying polyurethane hard foam is used as the foaming agent, the water resistance of the catalyst is very high, and the common organotin catalyst cannot meet the requirement.

Disclosure of Invention

The invention aims to solve the problems of short service life, poor catalytic effect and the like caused by high toxicity, easy hydrolysis failure and the like of a catalyst sprayed with polyurethane hard foam, and provides an inorganic active ingredient catalyst, a preparation method and application thereof.

In order to achieve the above object, the technical scheme of the present invention is as follows.

A first aspect of the present invention provides a metal oxide composite catalytic material comprising a support and an active ingredient supported on the support; the carrier is any one of alumina, zirconia, silica, activated carbon and graphite.

In a preferred embodiment, the active ingredient is any one or a combination of two of antimony oxide, tin oxide, bismuth oxide and iron oxide.

In a preferred embodiment, the mass ratio of the active ingredient to the carrier is 5 to 20: 80-95%.

In a preferred embodiment, the mass ratio of the active ingredient to the carrier is 10 to 15: 85-90.

In a preferred embodiment, the metal oxide composite catalytic material further comprises a binder, the binder being PVA.

In a preferred embodiment, the carrier has a particle size of 1 to 20 μm; the particle size of the active ingredient is 5-100 nm.

The second aspect of the present invention provides a method for preparing a metal oxide composite catalytic material, where the metal oxide composite catalytic material is the metal oxide composite catalytic material provided in the first aspect, and the specific preparation method includes the following steps:

dispersing the active ingredient in the water solution, then adding the carrier, uniformly mixing, and filtering to obtain the metal oxide composite catalytic material.

In a preferred embodiment, the aqueous solution is an aqueous PVA solution, and the mass percentage of the aqueous PVA solution is 1%.

In a third aspect, the present invention provides the use of a metal oxide composite catalytic material as a catalyst for the preparation of polyurethane rigid foam materials. The metal oxide composite catalytic material is the metal oxide composite catalytic material provided in the first aspect.

In a preferred embodiment, the raw materials for preparing the polyurethane rigid foam material comprise polyether polyol, polyester polyol and catalyst; the catalyst accounts for 1.5 to 1.9 percent of the total mass of the polyether polyol and the polyester polyol.

In a preferred embodiment, the polyurethane hard foam material is prepared from the following raw materials in parts by weight: (1) a combination polyether: 30 parts of polyether polyol 4110, 70 parts of polyester polyol 3152, 1.5-1.9 parts of solid composite catalyst, 1.2-1.4 parts of potassium acetate catalyst, 1.8 parts of silicone oil, 20 parts of flame retardant, 6 parts of synergistic flame retardant, 23 parts of foaming agent and 5 parts of stabilizer; (2) 162 parts of polymeric isocyanate.

In a preferred embodiment, the flame retardant is a liquid flame retardant and/or a solid flame retardant;

the liquid flame retardant is one or a combination of more of chlorinated paraffin, dimethyl methylphosphonate, diethyl ethylphosphonate and triethyl phosphate;

the solid flame retardant is one or a combination of a plurality of microcapsule red phosphorus, melamine phosphate, diethyl aluminum hypophosphite, expandable graphite and melamine cyanurate.

In a preferred embodiment, the synergistic flame retardant is triethyl phosphate; the foaming agent is pentafluoropropane (245 FA); the stabilizer is sol-type silicon dioxide.

In a preferred embodiment, the preparation method of the polyurethane hard foam material comprises the following steps:

The method comprises the steps of preparing the combined polyether according to a proportion, directly purchasing polymeric isocyanate, and enabling the combined polyether and the polymeric isocyanate to be obtained through a plunger pump according to a volume ratio of 1: and 1, atomizing and uniformly mixing under the action of high-pressure gas, spraying on the surface of a building, and foaming, curing and curing to obtain the polyurethane hard foam material.

The invention has the beneficial effects that:

1. according to the invention, the inert material is used as a carrier, the metal oxide is dispersed on the surface of the inert material to obtain the solid catalyst, and the solid catalyst is used for preparing the polyurethane hard foam by replacing a liquid catalyst commonly used in the market, so that the catalytic effect can be improved, and the cost can be greatly reduced.

2. According to the invention, the nano active ingredients are loaded on the surface of the micron-sized inert material, so that the dispersion performance is improved under the condition of reducing the dosage of the active ingredients.

3. Compared with a commercially available liquid catalyst, the metal oxide composite catalytic material prepared by the invention can be uniformly dispersed in the polyurethane hard foam material, so that the crosslinking density and the thermal decomposition temperature of the polyurethane hard foam material are improved, the compressive strength and the high-low temperature dimensional stability of the polyurethane hard foam material are further improved, and meanwhile, the cost is greatly reduced.

Drawings

FIG. 1 is a scanning electron micrograph of a polyurethane rigid foam material prepared in application example 10 of the present invention. Wherein, (A) is a 1000-time picture of a scanning electron microscope; and (B) is a 2000 times photograph of a scanning electron microscope.

Detailed Description

The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.

All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

Based on the research on the performance of the existing spray polyurethane hard foam catalyst, it is necessary to provide one or a series of catalysts which have high cost performance, are safe, nontoxic and long in service life, and can be well dissolved in the combined polyether. In addition, the use of the foaming agent 141b commonly used at present is totally forbidden in 2025, water is used as a chemical foaming agent instead of 141b in the combined polyether, the use amount of the all-water spraying polyurethane hard foam is gradually increased, even the all-water spraying polyurethane hard foam is used as the foaming agent, the water resistance of the catalyst is very high, and the common organotin catalyst cannot meet the requirement.

With this technology and market demand, the present invention has been made to solve the above problems using a solid catalyst. The spray-type polyurethane hard foam material uses a solid catalyst, and the choice range is wide, and in consideration of the catalytic activity and cost performance, the best catalytic effect metal oxide, such as tin and bismuth oxide, is preferred. The metal oxide, especially the transition metal oxide, has very good chemical stability and no problem of hydrolysis and deterioration; and they are all non-toxic. In contrast, organotin and organobismuth are extremely toxic, e.g., tetraethyltin lethal amounts of 16mg/kg per rat oral site, and use of organotin has been explicitly limited internationally, e.g., to a maximum allowable concentration of 0.1mg/m ³ for organotin per prescribed percutaneous absorption operating environment. Tin oxide is completely nontoxic, various tin ware products are widely applied to tableware, and the tin oxide is widely applied to facial masks, facial cleanser and emulsion at present; tin oxide and bismuth oxide are also only about 1/6 of the price of organotin.

Of course, the use of solid catalysts, metal oxide composite polyethers, is also a critical issue, and the present invention essentially solves these problems, thereby enabling the use of solid metal oxide catalysts. There are two main problems: firstly, the interface problem of the reaction is that the liquid catalyst is dissolved in the combined polyether and dispersed in a molecular form; the reaction interface is very large; the solid catalyst is fine particles, the space structure is much larger than that of molecules, and therefore, the dosage of the solid catalyst is very large; secondly, the problem of uniform dispersion is solved, and the solid catalyst is agglomerated and precipitated, so that the phenomenon of nonuniform dispersion in liquid combined polyether is caused.

Firstly, the problem of the amount of the solid catalyst to be used. It is known in the art that the reaction between a solid catalyst and a liquid reactant is a heterogeneous catalytic reaction, and the reaction is concentrated in the interfacial region of two phases, so that the larger the interfacial region is, the better the larger the specific surface area of the solid catalyst is, the smaller the particle size is, but the smaller the particle size is, and the higher the production cost is. The problem of catalyst dosage can be well solved by adjusting the particle size of the solid catalyst.

Secondly, the problem of dispersion of the solid catalyst can be solved temporarily by stirring, but after the stirring is stopped, the solid catalyst precipitates due to the density difference between the solid catalyst and the polyether composition, and therefore, the density difference between the two needs to be adjusted. The invention solves the problem of precipitation of the solid catalyst by bonding the solid catalyst to the surface of the low-density material and adjusting the density of the whole solid powder to be consistent with that of the combined polyether. Moreover, because of the carrier, the catalyst is prevented from forming hard agglomeration due to the excessively large specific surface area, even if the catalyst is slightly precipitated, and the catalyst can be uniformly dispersed in the combined polyether again by slightly stirring before use.

The invention selects amorphous metal oxides, which swell in the weak-polarity polyether polyol, the density is greatly reduced, and the consistency of the density of the solid powder loaded with the catalyst and the density of the combined polyether can be realized by controlling the proportion of the catalyst and the catalyst with larger density and the density adjustment of the combined polyether, thereby solving the problem of precipitation. The porous activated carbon and the porous graphite (micro-expanded graphite) can be loaded on the surfaces, because of the porous structure, the pores of the porous activated carbon and the porous graphite are closed by a high-viscosity binder in the loading process to form a closed pore structure, so that the density can be adjusted by adjusting the porosity, the density of the solid catalyst can be adjusted, the problem can be solved, and the carriers are all high-inertia inorganic materials, so that the flame retardance of the polyurethane rigid foam is obviously improved.

The first aspect of the present invention provides a metal oxide composite catalytic material, which is advantageous for dispersion and cost reduction by nanocrystallizing the active ingredient and then loading the active ingredient on the surface of the micron-sized inert material, while the dosage of the active ingredient is reduced, for example, commercially available stannous octoate is 50-70 ten thousand/ton, and the nano-tin oxide adopted by the present invention is only 10-15 ten thousand/ton.

A first aspect of the present invention provides a metal oxide composite catalytic material comprising a support and an active ingredient supported on the support; the carrier is any one of alumina, zirconia, silica, activated carbon and graphite. Preferably, the carrier is any one of alumina, silica, activated carbon and graphite.

In a preferred embodiment, the active ingredient is any one or a combination of two of antimony oxide, tin oxide, bismuth oxide and iron oxide. Preferably, the carrier is tin oxide and/or bismuth oxide.

In a preferred embodiment, the mass ratio of the active ingredient to the carrier is 5 to 20: 80-95%. For example, 5: 95. 10: 90. 12: 88. 15: 85. 20:80, etc.

In a preferred embodiment, the metal oxide composite catalytic material is prepared by dispersing an active ingredient in an aqueous solution, and then uniformly mixing the active ingredient with a carrier; the aqueous solution is PVA aqueous solution, and the mass percentage of the PVA aqueous solution is 1%.

In a preferred embodiment, the carrier has a particle size of 3 to 7 μm; the particle size of the active ingredient is 20-40 nm.

In a preferred embodiment, the polyurethane hard foam material is prepared from the following raw materials in parts by weight:

(1) And (3) combined polyether: 30 parts of polyether polyol 4110, 70 parts of polyester polyol 3152, 1.5-1.9 parts of solid composite catalyst, 1.2-1.4 parts of potassium acetate catalyst, 1.8 parts of silicone oil, 20 parts of flame retardant, 6 parts of synergistic flame retardant, 23 parts of foaming agent and 5 parts of stabilizer; (2) 162 parts of polymeric isocyanate.

In a preferred embodiment, the polyurethane rigid foam material contains a flame retardant, wherein the flame retardant is a liquid flame retardant and/or a solid flame retardant;

The polyurethane rigid foam material prepared by the invention can also improve the flame retardant property and reduce the smoke quantity.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.

It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.

In the following embodiments of the invention, the rotation speed of high-speed stirring is 1000-1500 rpm; the rotation speed of low-speed stirring is 100-500 rpm.

In the following application examples of the invention, the flame retardant is melamine phosphate, and the synergistic flame retardant is triethyl phosphate; the foaming agent is pentafluoropropane (245 FA); the stabilizer is sol-type silicon dioxide.

The methods described in the examples below are conventional, unless otherwise specified; the reagents and materials are commercially available unless otherwise specified.

Example 1

A metal oxide composite catalytic material comprising a support and an active ingredient supported on the support; the carrier is alumina, and the active ingredient is tin oxide. The mass ratio of the active component to the carrier is 10:90. the particle size of the carrier is 3-7 mu m; the particle size of the active ingredient is 20-40 nm.

The preparation method of the metal oxide composite catalytic material comprises the following steps:

Adding 10g of tin oxide into 30mL of PVA water solution with the mass percentage of 1%, stirring at a high speed at 1000 rpm for uniform dispersion, then adding 90g of aluminum oxide, stirring at a low speed at 300 rpm for uniform mixing, and then performing filter pressing, drying and air flow grinding to obtain the metal oxide composite catalytic material.

Example 2

A metal oxide composite catalytic material comprising a support and an active ingredient supported on the support; the carrier is alumina, and the active ingredient is tin oxide. The mass ratio of the active component to the carrier is 12:88. the particle size of the carrier is 3-7 mu m; the particle size of the active ingredient is 20-40 nm.

adding 12g of tin oxide into 36mL of PVA aqueous solution with the mass percentage of 1%, stirring at a high speed, dispersing uniformly, adding 88g of aluminum oxide, stirring, mixing uniformly, press-filtering, drying and grinding by a jet mill to obtain the metal oxide composite catalytic material.

Example 3

A metal oxide composite catalytic material comprising a support and an active ingredient supported on the support; the carrier is alumina, and the active ingredient is tin oxide. The mass ratio of the active component to the carrier is 15:85. the particle size of the carrier is 3-7 mu m; the particle size of the active ingredient is 20-40 nm.

Adding 15g of tin oxide into 45mL of PVA water solution with the mass percentage of 1%, stirring at a high speed, dispersing uniformly, then adding 85g of aluminum oxide, stirring, mixing uniformly, press-filtering, drying and grinding by a pneumatic mill to obtain the metal oxide composite catalytic material.

Example 4

A metal oxide composite catalytic material comprising a support and an active ingredient supported on the support; the carrier is alumina, and the active ingredient is tin oxide. The mass ratio of the active component to the carrier is 20:80. the particle size of the carrier is 3-7 mu m; the particle size of the active ingredient is 20-40 nm.

Adding 20g of tin oxide into 15mL of PVA water solution with the mass percentage of 1%, stirring at a high speed, dispersing uniformly, adding 80g of aluminum oxide, stirring, mixing uniformly, press-filtering, drying and grinding by a jet mill to obtain the metal oxide composite catalytic material.

Example 5

A metal oxide composite catalytic material comprising a support and an active ingredient supported on the support; the carrier is alumina, and the active ingredient is tin oxide. The mass ratio of the active component to the carrier is 5:95. the particle size of the carrier is 3-7 mu m; the particle size of the active ingredient is 20-40 nm.

Adding 5g of tin oxide into 15mL of PVA water solution with the mass percentage of 1%, stirring at a high speed, dispersing uniformly, adding 95g of aluminum oxide, stirring, mixing uniformly, press-filtering, drying and grinding by a jet mill to obtain the metal oxide composite catalytic material.

Example 6

A metal oxide composite catalytic material comprising a support and an active ingredient supported on the support; the carrier is alumina, and the active ingredient is bismuth oxide. The mass ratio of the active component to the carrier is 15:85. the particle size of the carrier is 3-7 mu m; the particle size of the active ingredient is 20-40 nm.

Adding 15g of bismuth oxide into 45mL of PVA water solution with the mass percentage of 1%, stirring at a high speed, dispersing uniformly, then adding 85g of aluminum oxide, stirring, mixing uniformly, press-filtering, drying and grinding by a pneumatic mill to obtain the metal oxide composite catalytic material.

Example 7

A metal oxide composite catalytic material comprising a support and an active ingredient supported on the support; the carrier is zirconia, and the active ingredient is bismuth oxide. The mass ratio of the active component to the carrier is 15:85. the particle size of the carrier is 3-7 mu m; the particle size of the active ingredient is 20-40 nm.

Adding 15g of bismuth oxide into 45mL of PVA water solution with the mass percentage of 1%, stirring at a high speed, dispersing uniformly, then adding 85g of zirconium oxide, stirring, mixing uniformly, press-filtering, drying and grinding by a pneumatic mill to obtain the metal oxide composite catalytic material.

Example 8

A metal oxide composite catalytic material comprising a support and an active ingredient supported on the support; the carrier is silicon dioxide, and the active ingredient is bismuth oxide. The mass ratio of the active component to the carrier is 15:85. the particle size of the carrier is 3-7 mu m; the particle size of the active ingredient is 20-40 nm.

Adding 15g of bismuth oxide into 45mL of PVA water solution with the mass percentage of 1%, stirring at a high speed, dispersing uniformly, adding 85g of silicon dioxide, stirring, mixing uniformly, press-filtering, drying and grinding by a pneumatic mill to obtain the metal oxide composite catalytic material.

Example 9

A metal oxide composite catalytic material comprising a support and an active ingredient supported on the support; the carrier is active carbon, and the active component is bismuth oxide. The mass ratio of the active component to the carrier is 15:85. the particle size of the carrier is 3-7 mu m; the particle size of the active ingredient is 20-40 nm.

Adding 15g of bismuth oxide into 45mL of PVA water solution with the mass percentage of 1%, stirring at a high speed, dispersing uniformly, adding 85g of active carbon, stirring, mixing uniformly, press-filtering, drying and grinding by a pneumatic mill to obtain the metal oxide composite catalytic material.

Example 10

A metal oxide composite catalytic material comprising a support and an active ingredient supported on the support; the carrier is graphite, and the active ingredient is bismuth oxide. The mass ratio of the active component to the carrier is 15:85. the particle size of the carrier is 3-7 mu m; the particle size of the active ingredient is 20-40 nm.

adding 15g of bismuth oxide into 45mL of PVA water solution with the mass percentage of 1%, stirring at a high speed, dispersing uniformly, then adding 85g of graphite, stirring, mixing uniformly, press-filtering, drying and grinding by a pneumatic mill to obtain the metal oxide composite catalytic material.

Example 11

A metal oxide composite catalytic material comprising a support and an active ingredient supported on the support; the carrier is alumina; the active ingredients are tin oxide and bismuth oxide, and the mass ratio of the tin oxide to the bismuth oxide is 1:1. the mass ratio of the active component to the carrier is 15:85. the particle size of the carrier is 3-7 mu m; the particle size of the active ingredient is 20-40 nm.

7.5g of tin oxide and 7.5g of bismuth oxide are added into 45mL of PVA water solution with the mass percentage of 1%, and are stirred and dispersed uniformly at a high speed, then 85g of aluminum oxide is added, and after being stirred and mixed uniformly, the metal oxide composite catalytic material is obtained through filter pressing, drying and air flow grinding.

Example 12

A metal oxide composite catalytic material comprising a support and an active ingredient supported on the support; the carrier is alumina; the active ingredients are tin oxide and bismuth oxide, and the mass ratio of the tin oxide to the bismuth oxide is 1:2. the mass ratio of the active component to the carrier is 15:85. the particle size of the carrier is 3-7 mu m; the particle size of the active ingredient is 20-40 nm.

Adding 5g of tin oxide and 10g of bismuth oxide into 45mL of PVA aqueous solution with the mass percentage of 1%, stirring at a high speed, dispersing uniformly, adding 85g of aluminum oxide, stirring, mixing uniformly, press-filtering, drying and grinding by a jet mill to obtain the metal oxide composite catalytic material.

Example 13

A metal oxide composite catalytic material comprising a support and an active ingredient supported on the support; the carrier is alumina; the active ingredients are tin oxide and bismuth oxide, and the mass ratio of the tin oxide to the bismuth oxide is 1:4. the mass ratio of the active component to the carrier is 15:85. the particle size of the carrier is 3-7 mu m; the particle size of the active ingredient is 20-40nm.

3g of tin oxide and 12g of bismuth oxide are added into 45mL of PVA aqueous solution with the mass percentage of 1%, stirred and dispersed uniformly at high speed, then 85g of aluminum oxide is added, stirred and mixed uniformly, and then the mixture is subjected to pressure filtration, drying and air flow grinding, so that the metal oxide composite catalytic material is obtained.

Example 14

A metal oxide composite catalytic material comprising a support and an active ingredient supported on the support; the carrier is alumina; the active ingredients are tin oxide and bismuth oxide, and the mass ratio of the tin oxide to the bismuth oxide is 4:1. the mass ratio of the active component to the carrier is 15:85. the particle size of the carrier is 3-7 mu m; the particle size of the active ingredient is 20-40nm.

adding 12g of tin oxide and 3g of bismuth oxide into 45mL of PVA aqueous solution with the mass percentage of 1%, stirring at a high speed, dispersing uniformly, adding 85g of aluminum oxide, stirring, mixing uniformly, press-filtering, drying and grinding by a jet mill to obtain the metal oxide composite catalytic material.

Example 15

A metal oxide composite catalytic material comprising a support and an active ingredient supported on the support; the carrier is alumina, and the active ingredient is antimony oxide. The mass ratio of the active component to the carrier is 15:85. the particle size of the carrier is 3-7 mu m; the particle size of the active ingredient is 20-40 nm.

15g of antimony oxide is added into 45mL of PVA water solution with the mass percentage of 1%, and is stirred and dispersed uniformly at a high speed, then 85g of alumina is added, and after being stirred and mixed uniformly, the mixture is subjected to filter pressing, drying and air flow grinding, so that the metal oxide composite catalytic material is obtained.

Example 16

Application example 1

A polyurethane hard foam material is prepared from the following raw materials in parts by weight:

(1) And (3) combined polyether: 30 parts of polyether polyol 4110, 70 parts of polyester polyol 3152, 1.5 parts of solid composite catalyst, 1.4 parts of potassium acetate catalyst, 1.8 parts of silicone oil, 20 parts of flame retardant, 6 parts of synergistic flame retardant, 23 parts of foaming agent and 5 parts of stabilizer; (2) 162 parts of polymeric isocyanate;

the solid composite catalyst is the metal oxide composite catalytic material of example 1.

The preparation method of the polyurethane hard foam material comprises the following steps:

Mixing and preparing the combined polyether according to the proportion; the polymeric isocyanate is obtained by direct purchase; the combined polyether and polymeric isocyanate are pumped through a plunger pump according to a volume ratio of 1: and 1, atomizing and uniformly mixing under the action of high-pressure gas, spraying on the surface of a building, and foaming, curing and curing to obtain the polyurethane rigid foam material.

Application example 2

(1) And (3) combined polyether: 30 parts of polyether polyol 4110, 70 parts of polyester polyol 3152, 1.5 parts of solid composite catalyst, 1.4 parts of potassium acetate catalyst, 1.8 parts of silicone oil, 20 parts of flame retardant, 6 parts of synergistic flame retardant, 23 parts of foaming agent and 5 parts of stabilizer; (2) 162 parts of polymeric isocyanate.

The solid composite catalyst is the metal oxide composite catalytic material of example 2.

Application example 3

The solid composite catalyst is the metal oxide composite catalytic material of example 3.

Application example 4

The solid composite catalyst is the metal oxide composite catalytic material of example 4.

Application example 5

The solid composite catalyst is the metal oxide composite catalytic material of example 5.

Application example 6

(1) And (3) combined polyether: 30 parts of polyether polyol 4110, 70 parts of polyester polyol 3152, 1.9 parts of solid composite catalyst, 1.2 parts of potassium acetate catalyst, 1.8 parts of silicone oil, 20 parts of flame retardant, 6 parts of synergistic flame retardant, 26 parts of foaming agent and 3 parts of stabilizer; (2) 162 parts of polymeric isocyanate.

The solid composite catalyst is the metal oxide composite catalytic material of example 6.

Application example 7

The solid composite catalyst is the metal oxide composite catalytic material of example 7.

Application example 8

The solid composite catalyst is the metal oxide composite catalytic material of example 8.

Application example 9

The solid composite catalyst is the metal oxide composite catalytic material of example 9.

Application example 10

The solid composite catalyst is the metal oxide composite catalytic material of example 10.

Application example 11

(1) And (3) combined polyether: 30 parts of polyether polyol 4110, 70 parts of polyester polyol 3152, 1.5 parts of solid composite catalyst, 1.2 parts of potassium acetate catalyst, 1.8 parts of silicone oil, 20 parts of flame retardant, 6 parts of synergistic flame retardant, 21 parts of foaming agent and 4 parts of stabilizer; (2) 162 parts of polymeric isocyanate.

The solid composite catalyst was the metal oxide composite catalytic material of example 11.

Application example 12

The solid composite catalyst is the metal oxide composite catalytic material of example 12.

Application example 13

The solid composite catalyst is the metal oxide composite catalytic material of example 13.

Application example 14

(1) And (3) combined polyether: 30 parts of polyether polyol 4110, 70 parts of polyester polyol 3152, 1.5 parts of solid composite catalyst, 1.2 parts of potassium acetate catalyst, 1.8 parts of silicone oil, 20 parts of flame retardant, 6 parts of synergistic flame retardant, 21 parts of foaming agent and 4 parts of stabilizer; (2) 162 parts of polymeric isocyanate. The solid composite catalyst is the metal oxide composite catalytic material of example 14.

Application example 15

A polyurethane hard foam material is prepared from the following raw materials in parts by weight: (1) a combination polyether: 30 parts of polyether polyol 4110, 70 parts of polyester polyol 3152, 1.5 parts of solid composite catalyst, 1.2 parts of potassium acetate catalyst, 1.8 parts of silicone oil, 20 parts of flame retardant, 6 parts of synergistic flame retardant, 21 parts of foaming agent and 4 parts of stabilizer; (2) 162 parts of polymeric isocyanate

The solid composite catalyst is the metal oxide composite catalytic material of example 15.

Application example 16

The solid composite catalyst was the metal oxide composite catalytic material of example 16.

Comparative example 1 was used

(1) And (3) combined polyether: 30 parts of polyether polyol 4110, 70 parts of polyester polyol 3152, 1.2 parts of solid composite catalyst, 1.2 parts of potassium acetate catalyst, 1.8 parts of silicone oil, 20 parts of flame retardant, 6 parts of synergistic flame retardant, 21 parts of foaming agent and 4 parts of stabilizer; (2) 162 parts of polymeric isocyanate.

The solid composite catalyst is prepared from tin oxide and silicon dioxide in a mass ratio of 15: 85.

Comparative example 2 was used

The solid composite catalyst is prepared from bismuth oxide and aluminum oxide in a mass ratio of 15: 85.

Comparative example 3 was used

The solid composite catalyst is prepared from tin oxide, bismuth oxide and silicon dioxide in a mass ratio of 7.5:7.5: 85.

Comparative example 4 was used

The solid composite catalyst is prepared from tin oxide, bismuth oxide and graphite in a mass ratio of 7.5:7.5: 85.

Comparative example 5 was used

(1) And (3) combined polyether: 30 parts of polyether polyol 4110, 70 parts of polyester polyol 3152, 1.2 parts of liquid catalyst, 1.2 parts of potassium acetate catalyst, 1.8 parts of silicone oil, 20 parts of flame retardant, 6 parts of synergistic flame retardant, 21 parts of foaming agent and 4 parts of stabilizer; (2) 162 parts of polymeric isocyanate.

The liquid catalyst is a solution of stannous octoate in diethylene glycol, and the stannous octoate content is 15%.

The mass ratios of the respective substances in the above examples are shown in tables 1 to 3.

TABLE 1 mass ratio of each substance in examples 1 to 5

Examples	Active ingredient	Carrier body	Mass ratio ^a
				1	Tin oxide	Alumina oxide	10：90
2	Tin oxide	Alumina oxide	12：88
				3	Tin oxide	Alumina oxide	15：85
4	Tin oxide	Alumina oxide	20：80
				5	Tin oxide	Alumina oxide	5：95

TABLE 2 mass fractions of the substances of examples 6 to 10

Examples	Active ingredient	Carrier body	Mass ratio ^a
				6	Bismuth oxide	Alumina oxide	15：85
7	Bismuth oxide	Zirconia (zirconia)	15：85
				8	Bismuth oxide	Silica dioxide	15：85
9	Bismuth oxide	Activated carbon	15：85
				10	Bismuth oxide	Graphite	15：85

TABLE 3 mass ratios of the substances of examples 3, 6 and 11 to 14

Note that: the mass ratio ^a is the mass ratio of the active ingredient to the carrier.

Test 1: and (5) testing physical properties of the polyurethane hard foam material.

The following physical properties were measured on the polyurethane rigid foam materials prepared in the above application examples, and the results are shown in tables 4 to 7.

TABLE 4 influence of different ratios of active ingredient to carrier on the properties of polyurethane hard foam materials

From the results in Table 4, it can be seen that the reaction time (milky white, gel and debonding) of each stage was significantly shortened as the content of the active ingredient tin oxide increased from 5% to 20%, indicating that the corresponding catalyst prepared was able to significantly increase the reaction rate as the content of the active ingredient tin oxide increased. For the density and the heat conductivity of the finished product, the more the catalyst active ingredients are, the faster the reaction is, the larger the heat release amount is, the faster and more sufficient the foaming agent is vaporized, so the lower the density is, the lower the corresponding heat conductivity is; but the compressive strength not only depends on the density of the product, but also depends on the reaction degree, the more the catalyst active ingredients are, the more thoroughly the reaction is, the molecular crosslinking degree is high, the compressive strength is good, but the density is also reduced, and the compressive strength is weakened.

TABLE 5 Effect of different Carriers on the Properties of polyurethane hard foam materials

Since bismuth oxide is less catalytically active than tin oxide, it is used in an amount of 1.9 parts, more than 1.5 parts of tin oxide, in order to achieve the same catalytic effect. It is clear from Table 5 that different carriers have an influence on the reaction rate, wherein the catalytic effect of graphite and activated carbon is inferior because they are porous structures, bismuth oxide and a small amount of catalyst are enclosed in the voids during their compounding, resulting in a decrease in the active ingredient, but the influence is not large overall, and the relative deviation of each index is within 10%.

TABLE 6 influence of different active ingredients on the Properties of polyurethane hard foam Material

As can be seen from the results of table 6, the catalytic activities of the three oxides were in turn as follows, as can be seen from a comparative analysis of the opalescence, gel and debonding times: tin oxide > bismuth oxide > antimony oxide. We have also tried to make metal oxide composite catalytic materials using iron oxide, but experimental results found that the catalytic activities of the two oxides were in turn: antimony oxide > iron oxide. Since the catalytic activity of iron oxide is relatively poor, we have not used iron oxide. Tin oxide, bismuth oxide and antimony oxide have good synergistic effect, and the mass ratio of the tin oxide to the bismuth oxide is 1:1, the catalytic effect is best, the reaction time is shortest, and the compression resistance effect is best.

TABLE 7 Effect of different metal oxide composite catalytic materials on the Performance of polyurethane hard foam materials

As can be seen from Table 7, the liquid catalyst stannous octoate has good catalytic effect, and the same dosage is superior to that of the solid tin oxide catalyst, namely, the solid tin oxide catalyst and the bismuth oxide tin oxide 1:1 the effect of the composition is basically the same; this demonstrates that the same catalytic effect can be achieved with a solid catalyst, which fully takes advantage of the safety, non-toxicity and low cost of the solid catalyst. From comparative examples 1-3, their catalytic ability was tin oxide/bismuth oxide > tin oxide > bismuth oxide, in accordance with the foregoing; in connection with comparative example 4, the carrier had a certain effect on the activity of the catalyst, but was not large. It is worth to say that, on the surface of a great deal of research, graphite has a good effect on flame retardance of polyurethane rigid foam, so in the field of high flame retardance, graphite is selected as a carrier, and although certain catalytic activity is lost, the high flame retardance is also significant.

Application example 3 the cost of preparing polyurethane rigid foam material with nano tin oxide was compared with the cost of preparing polyurethane rigid foam material with stannous octoate of application comparative example 5, wherein the cost of stannous octoate was 50-70 ten thousand/ton, and the cost of nano tin oxide was only 10-15 ten thousand/ton. By comparison, the polyurethane hard foam material prepared by using the nano tin oxide in the embodiment 3 is beneficial to dispersion performance and cost reduction while the dosage is reduced by loading the nano tin oxide on the surface of the inert material.

Test 2: and (5) testing flame retardant property.

The flame retardant properties of the polyurethane rigid foam materials prepared in the above application examples were tested as follows. The flame retardant property of the polyurethane rigid foam material is evaluated, and the most common use is oxygen index detection, and the detection results are shown in table 8:

TABLE 8 influence of catalysts and supports on flame retardant Properties of polyurethane hard foam

It can be seen from table 8 that the effect on the oxygen index is small, whether it is a liquid catalyst or a solid catalyst, because the catalyst only changes the reaction rate and does not change the intrinsic molecular structure, and thus has little effect on the flame retardant properties. However, the graphite carrier, whose burning point is 950 ℃ and thus is not flammable in a conventional 650 ℃ flame, has a laminar structure and can overlap each other during combustion to form a laminated barrier. In contrast, other carriers have a fine powder structure and cannot overlap each other, and thus flame is prevented from being burned inward due to a barrier layer formed by the graphite carrier, thereby improving flame retardant performance (oxygen index increase) thereof, compared with other carriers. Numerous documents and patents have demonstrated that graphite can improve the flame retardant properties of polyurethane rigid foams.

Test 3: microscopic test

Scanning electron microscopy tests were performed on the metal oxide composite catalytic material prepared in example 10, and specific results are shown in fig. 1.

As can be seen from FIG. 1, the polyurethane hard foam material successfully prepared by the application of the embodiment 10 of the invention is prepared by taking a graphite-loaded solid catalyst as a raw material, and the polyurethane hard foam material contains graphite with a lamellar structure, which is helpful for improving the flame retardant property of the polyurethane hard foam.

In summary, in the above embodiments of the present invention, after the nano active ingredient is ultrasonically dispersed in water, the nano active ingredient is loaded on the surface of inert inactive ingredient, and the polyurethane hard foam active ingredient catalyst is obtained after drying and crushing. By adding the catalyst into the traditional combined polyether, the crosslinking density, the molecular weight, the thermal decomposition temperature and the like of the polyurethane hard foam are greatly improved, and the compressive strength and the high-low temperature dimensional stability of the polyurethane hard foam are further improved; simultaneously, the flame retardance is improved, and the smoke quantity is reduced.

The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.

Claims

1. A metal oxide composite catalytic material, characterized by comprising a carrier and an active ingredient supported on the carrier; the carrier is any one of alumina, zirconia, silicon dioxide, activated carbon and graphite; the active ingredient is tin oxide;

The mass ratio of the active component to the carrier is 5-20: 80-95 percent;

the particle size of the carrier is 1-20 mu m; the particle size of the active ingredient is 5-100 nm.

2. The metal oxide composite catalytic material according to claim 1, wherein the mass ratio of the active component to the carrier is 10 to 15: 85-90.

3. The metal oxide composite catalytic material of claim 1, further comprising a binder, the binder being PVA.

4. A method for preparing the metal oxide composite catalytic material according to claim 1, comprising the steps of:

5. The method for preparing a metal oxide composite catalytic material according to claim 4, wherein the aqueous solution is a PVA aqueous solution, and the mass percentage of the PVA aqueous solution is 1%.

6. Use of the metal oxide composite catalytic material of claim 1 as a catalyst for the preparation of polyurethane rigid foam materials.