阅读说明：本技术 一种聚氨酯硬泡保温材料及其制备方法 (Polyurethane hard foam heat-insulating material and preparation method thereof ) 是由 郭高显 林鹏 闫宇欣 陈伟 于 2021-08-06 设计创作，主要内容包括：本申请涉及保温材料技术领域,具体公开了一种聚氨酯硬泡保温材料及其制备方法。一种聚氨酯硬泡保温材料,由包括以下重量份的原料制备而成：A组分：聚醚多元醇95-140份、N,N-2-羟乙基氨甲基膦酸二乙酯48-55份、均泡剂2-6份、发泡剂20-50份、催化剂0.5-2.2份、硅烷偶联剂0.5-2份、抗氧化剂0.3-0.8份；B组分：异氰酸酯180-220份；C组分：碳酸钙粉体5-15份,碳酸钙粉体的平均粒径为1-2μm,碳酸钙粉体的活化度为95.0-99.9%。本申请的聚氨酯硬泡保温材料,具有保温性能优越、抗压强度高、阻燃性能好、使用寿命长的优点。(The application relates to the technical field of heat insulation materials, and particularly discloses a polyurethane hard foam heat insulation material and a preparation method thereof. The polyurethane hard foam heat-insulating material is prepared from the following raw materials in parts by weight: the component A comprises: 95-140 parts of polyether polyol, 48-55 parts of diethyl N, N-2-hydroxyethyl aminomethyl phosphonate, 2-6 parts of foam homogenizing agent, 20-50 parts of foaming agent, 0.5-2.2 parts of catalyst, 0.5-2 parts of silane coupling agent and 0.3-0.8 part of antioxidant; and B component: 180 portions of isocyanate and 220 portions; and C, component C: 5-15 parts of calcium carbonate powder, wherein the average grain diameter of the calcium carbonate powder is 1-2 mu m, and the activation degree of the calcium carbonate powder is 95.0-99.9%. The polyurethane rigid foam heat-insulating material has the advantages of excellent heat-insulating property, high compressive strength, good flame-retardant property and long service life.)

1. A polyurethane rigid foam thermal insulation material is characterized in that: the health-care food is prepared from the following raw materials in parts by weight:

the component A comprises: 95-140 parts of polyether polyol, 48-55 parts of diethyl N, N-2-hydroxyethyl aminomethyl phosphonate, 2-6 parts of foam homogenizing agent, 20-50 parts of foaming agent, 0.5-2.2 parts of catalyst, 0.5-2 parts of silane coupling agent and 0.3-0.8 part of antioxidant;

and B component: 180 portions of isocyanate and 220 portions;

and C, component C: 5-15 parts of calcium carbonate powder, wherein the average grain diameter of the calcium carbonate powder is 1-2 mu m, and the activation degree of the calcium carbonate powder is 95.0-99.9%.

2. The rigid polyurethane foam insulation material as set forth in claim 1, wherein: the health-care food is prepared from the following raw materials in parts by weight:

the component A comprises: 130 parts of polyether polyol 110-;

and B component: 190 and 210 parts of isocyanate;

and C, component C: 8-12 parts of calcium carbonate powder.

3. The rigid polyurethane foam insulation material as set forth in claim 1, wherein: the weight percentage of the calcium carbonate powder with the particle size less than 2 mu m is 68-88%, and the weight percentage of the calcium carbonate powder with the particle size less than 5 mu m is 92-99%.

4. The rigid polyurethane foam insulation material as set forth in claim 1, wherein: the calcium carbonate powder comprises the following components in percentage by weightThe components: CaCO₃97.1 to 97.7 percent of magnesium, 0.04 to 0.10 percent of MgO0 and the balance of impurities.

5. The rigid polyurethane foam insulation material as set forth in claim 1, wherein: the catalyst comprises the following components in percentage by weight (2-10): (12-3) Triethylamine and dibutyltin diisooctanoate.

6. The rigid polyurethane foam insulation material as set forth in claim 1, wherein: the water content of the calcium carbonate powder is less than 0.2 percent.

7. The rigid polyurethane foam insulation material as set forth in claim 1, wherein: the isocyanate comprises the following components in a weight ratio of (1.5-2.2): 1 with a polyphenylenepolymethylene polyisocyanate.

8. A method for preparing the polyurethane rigid foam thermal insulation material of any one of claims 1 to 7, which comprises the following steps:

s1, uniformly mixing the component A and the component C to obtain a primary mixed material;

s2, uniformly mixing the primary mixed material and the component B to obtain a mixed material, and putting the mixed material into a mold to obtain the heat-insulating material.

9. The method for preparing the polyurethane rigid foam thermal insulation material according to claim 8, wherein: and mixing the initial mixed material and the component B under the pressure of 0.4-0.7 MPa.

Technical Field

The application relates to the technical field of heat insulation materials, in particular to a polyurethane hard foam heat insulation material and a preparation method thereof.

Background

The polyurethane hard foam heat insulation material is a common heat insulation material, has a wide application range, is almost applied to various departments of national economy, currently covers various engineering fields such as furniture, automotive interior, building heat insulation, household appliances and the like, and is particularly widely applied to industrial building facilities in the aspect of building heat insulation, and is also increasingly applied to wall and roof heat insulation of civil building facilities and building air-conditioning pipeline systems in the aspect of building heat insulation.

The application of the polyurethane hard foam heat insulation material in the aspect of building heat insulation has higher requirements on the strength and the heat insulation performance of the heat insulation material, the common polyurethane hard foam heat insulation material is formed by mixing and foaming black and white composite materials, the black material is generally isocyanate, the white material is a mixture of polyol, a foaming agent and other additives, and the compressive strength of the mixture can generally reach about 240 kPa.

In view of the above-mentioned related art, the inventor believes that the strength of the polyurethane rigid foam insulation material is relatively low, and the polyurethane rigid foam insulation material is easily damaged, so that the service life of the polyurethane rigid foam insulation material is short.

Disclosure of Invention

In order to improve the strength of the polyurethane rigid foam heat-insulating material, the application provides the polyurethane rigid foam heat-insulating material and the preparation method thereof.

In a first aspect, the application provides a polyurethane rigid foam thermal insulation material, which adopts the following technical scheme:

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

the component A comprises: 95-140 parts of polyether polyol, 48-55 parts of diethyl N, N-2-hydroxyethyl aminomethyl phosphonate, 2-6 parts of foam homogenizing agent, 20-50 parts of foaming agent, 0.5-2.2 parts of catalyst, 0.5-2 parts of silane coupling agent and 0.3-0.8 part of antioxidant;

and B component: 180 portions of isocyanate and 220 portions;

and C, component C: 5-15 parts of calcium carbonate powder, wherein the average grain diameter of the calcium carbonate powder is 1-2 mu m, and the activation degree of the calcium carbonate powder is 95.0-99.9%.

By adopting the technical scheme, isocyanate and polyether glycol are subjected to polycondensation reaction under the action of a catalyst to obtain polyurethane, the polyurethane is foamed under the action of a foaming agent to form polyurethane hard bubbles, calcium carbonate powder is added in the reaction, and under the action of a silane coupling agent, an organic polyurethane material and inorganic powder can be effectively connected together, so that the calcium carbonate powder plays a role of a nucleation point when a foam cell structure in the polyurethane foaming process is formed, and the foam cell structure is formed by taking calcium carbonate powder particles as a center; the average particle size of calcium carbonate powder is controlled to be 1-2 mu m, the activation degree is controlled to be 95.0-99.9%, the calcium carbonate powder is fully dispersed in a polyurethane matrix, the calcium carbonate particles and polyurethane can be better combined, the diameter of cells is reduced, the density of the cells is increased, the cell wall of a rigid foam material is thickened, the compressive strength of the rigid foam polyurethane thermal insulation material is improved, the thermal insulation performance of the rigid foam polyurethane thermal insulation material can also be improved, the durability of the rigid foam polyurethane thermal insulation material is improved, the service life is prolonged, the probability that the thermal insulation material is changed due to the reduction of the performance is reduced, and the cost is saved.

In addition, the N, N-2-hydroxyethyl diethyl aminomethylphosphonate has certain flame retardant property and is matched with calcium carbonate powder, the calcium carbonate powder is used as an auxiliary agent of the N, N-2-hydroxyethyl diethyl aminomethylphosphonate, so that the energy of combustible materials during combustion is greatly reduced, the heat resistance of the polyurethane hard foam heat-insulating material is improved after the polyurethane hard foam heat-insulating material is heated, the polyurethane hard foam heat-insulating material is not easy to deform, carbon dioxide gas is generated after the calcium carbonate is heated and decomposed, the oxygen isolation is facilitated, the combustion time is delayed, and the flame retardant property of the polyurethane hard foam heat-insulating material is effectively improved.

Preferably, the polyurethane hard foam heat-insulating material is prepared from the following raw materials in parts by weight: the component A comprises: 130 parts of polyether polyol 110-;

and B component: 190 parts of a mixture of diphenylmethane diisocyanate (MDI) and polyphenylene polymethylene polyisocyanate (PAPI);

and C, component C: 8-12 parts of calcium carbonate powder, wherein the average grain diameter of the calcium carbonate powder is 1-2 mu m, and the activation degree of the calcium carbonate powder is 95.0-99.9%.

By adopting the technical scheme, the proportion among the raw materials is further optimized, and the overall performance of the polyurethane rigid foam heat-insulating material is improved.

Preferably, the weight ratio of the calcium carbonate powder with the particle diameter less than 2 μm is 68-88%, and the weight ratio of the calcium carbonate powder with the particle diameter less than 5 μm is 92-99%.

Through adopting above-mentioned technical scheme, with the particle size control of calcium carbonate powder at less within range for calcium carbonate powder granule is comparatively even, makes the in-process that the cell structure used calcium carbonate powder granule to form as the center, and the "nuclear point" of cell structure is more even, and the cell structure of formation is more even, improves the compactness and the homogeneity of cell structure, makes the cell wall thickening of hard bubble material, improves the compressive strength of polyurethane hard bubble insulation material.

Preferably, the calcium carbonate powder comprises the following components in percentage by weight: CaCO₃97.1 to 97.7 percent of magnesium, 0.04 to 0.10 percent of MgO0 and the balance of impurities.

By adopting the technical scheme, CaCO in calcium carbonate powder₃The content of the calcium carbonate is controlled at a higher level, namely the purity of the calcium carbonate powder is improved, and the effective action amount of the calcium carbonate powder can be improved; in addition, the MgO also has certain flame retardant property, so that the flame retardant property of the polyurethane rigid foam heat-insulating material can be ensured.

Preferably, the catalyst comprises (2-10) by weight: (12-3) Triethylamine and dibutyltin diisooctanoate.

By adopting the technical scheme, the tin catalyst is a catalyst commonly used in polyurethane hard foam, but the common tin catalyst is easy to agglomerate and precipitate after entering a foaming system.

Preferably, the water content of the calcium carbonate powder is less than 0.2%.

By adopting the technical scheme, the water content of the calcium carbonate powder is controlled at a lower level, and the introduction of water into a foaming system by the calcium carbonate powder is reduced, so that the layering probability of the foaming system is reduced, the normal operation of a foaming reaction is ensured, and the performance of the polyurethane hard foam heat-insulating material is ensured.

Preferably, the isocyanate comprises (1.5-2.2) by weight: 1 with a polyphenylenepolymethylene polyisocyanate.

In a second aspect, the application provides a preparation method of a polyurethane rigid foam thermal insulation material, which adopts the following technical scheme: a preparation method of a polyurethane rigid foam heat-insulating material comprises the following steps:

s1, uniformly mixing the component A and the component C in parts by weight to obtain a primary mixed material;

s2, uniformly mixing the primary mixed material and the component B according to the parts by weight to obtain a mixed material, and driving the mixed material into a mold to obtain the heat-insulating material.

By adopting the technical scheme, the calcium carbonate powder is mixed with the polyether glycol and then is mixed with the isocyanate, so that the calcium carbonate powder can be dispersed in a foaming system more uniformly, the uniformity of a cell structure taking the calcium carbonate powder as a core is improved, and the strength and the durability of the polyurethane hard foam heat-insulating material are improved.

Preferably, the primary mixed material and the component B are mixed under the pressure of 0.4-0.7 MPa.

By adopting the technical scheme, the foaming system becomes viscous and the density becomes large due to the addition of the calcium carbonate powder, and the proper increase of the pressure intensity is favorable for the full mixing of the raw materials in the foaming system.

In summary, the present application has the following beneficial effects:

1. the heat-insulating material is prepared by adding calcium carbonate powder with the average particle size of 1-2 mu m and the activation degree of 95.0-99.9 percent into a polyurethane foaming system in a matching way, wherein the heat-insulating material has the heat conductivity coefficient of 0.0237-0.0196W/m.k and the density of 35.1-38.7kg/m³The compressive strength is between 251 and 279Kpa, and the limiting oxygen index is between 32.4 and 35.7 percent; the heat insulation performance, the flame retardant performance and the compressive strength of the heat insulation material are improved, and the service life of the heat insulation material is prolonged.

2. According to the preparation method, the materials are mixed under a higher pressure, and the defect of uneven material mixing caused by the fact that the material density is increased due to the addition of the calcium carbonate powder is overcome.

Detailed Description

The present application will be described in further detail with reference to examples.

Raw materials

The foam homogenizing agent is a DC-201 type foam homogenizing agent;

the foaming agent is a cyclopentane foaming agent;

the antioxidant is 2, 6-di-tertiary-4-cresol;

the polyether polyol was 4410 polyether polyol, with a hydroxyl number of 440 and a molecular weight of 550.

Examples

Example 1

A polyurethane rigid foam thermal insulation material is prepared by the following method:

s1, uniformly mixing 95kg of polyether polyol, 55kg of diethyl N, N-2-hydroxyethylaminomethylphosphonate, 2kg of foam homogenizing agent, 50kg of foaming agent, 0.5kg of catalyst, 2kg of silane coupling agent, 0.3kg of antioxidant and 15kg of calcium carbonate powder to obtain a primary mixed material; the catalyst is stannous octoate;

the average grain diameter of the calcium carbonate powder is 1 mu m, and the activation degree of the calcium carbonate powder is 99.9 percent; the weight ratio of the calcium carbonate powder with the particle diameter less than 2 mu m is 50 percent, and the weight ratio of the calcium carbonate powder with the particle diameter less than 5 mu m is 80 percent; the calcium carbonate powder comprises the following components: CaCO₃97.1 percent, MgO 0.10 percent and the balance of impurities; the water content of the calcium carbonate powder was 0.5%.

S2, uniformly mixing the primary mixed material obtained in the step S1 with 180kg of diphenylmethane diisocyanate under normal pressure to obtain a mixed material, and driving the mixed material into a mold to obtain the heat-insulating material.

Example 2

The raw materials are mixed in different proportions from those in example 1, and the details are shown in Table 1.

TABLE 1 EXAMPLES 1-5 raw materials proportioning Table (kg)

	Example 1	Example 2	Example 3	Example 4	Example 5
						Polyether polyols	95	110	120	130	140
N, N-2-hydroxyethylaminomethylphosphonic acid diethyl ester	55	54	52	50	48
						Foam homogenizing agent	2	3	4	5	6
Foaming agent	50	45	30	25	20
						Catalyst and process for preparing same	0.5	1.0	1.4	1.6	2.2
Silane coupling agent	2	1.8	1.3	0.8	0.5
						Antioxidant agent	0.3	0.5	0.6	0.7	0.8
Diphenylmethane diisocyanate	180	190	200	210	220
						Calcium carbonate powder	15	12	10	8	5

Example 6

Unlike example 3, in step S2, the preliminary mixture obtained in S1 was mixed with 180kg of diphenylmethane diisocyanate under a pressure of 0.4MPa to obtain a mixed material.

Example 7

Unlike example 3, in step S2, the preliminary mixture obtained in S1 was mixed with 180kg of diphenylmethane diisocyanate under a pressure of 0.5MPa to obtain a mixed material.

Example 8

Unlike example 3, in step S2, the preliminary mixture obtained in S1 was mixed with 180kg of diphenylmethane diisocyanate under a pressure of 0.7MPa to obtain a mixed material.

Example 9

Unlike example 7, the calcium carbonate powder had an average particle diameter of 1.5 μm, a powder weight ratio of the calcium carbonate powder having a particle diameter of less than 2 μm was 50%, and a powder weight ratio of the calcium carbonate powder having a particle diameter of less than 5 μm was 80%.

Example 10

Unlike example 7, the calcium carbonate powder had an average particle size of 2 μm, a powder weight ratio of the calcium carbonate powder having a particle size of less than 2 μm was 50%, and a powder weight ratio of the calcium carbonate powder having a particle size of less than 5 μm was 80%.

Example 11

Unlike example 9, the degree of activation of the calcium carbonate powder was 97.5%.

Example 12

Unlike example 9, the degree of activation of the calcium carbonate powder was 95.0%.

Example 13

Unlike example 11, the calcium carbonate powder contained 68% by weight of a powder having a particle size of less than 2 μm and 99% by weight of a powder having a particle size of less than 5 μm.

Example 14

Unlike example 11, the calcium carbonate powder contained 78% by weight of powder having a particle size of less than 2 μm and 95% by weight of powder having a particle size of less than 5 μm.

Example 15

Unlike example 11, the calcium carbonate powder contained 88% by weight of powder having a particle size of less than 2 μm and 92% by weight of powder having a particle size of less than 5 μm.

Example 16

Unlike example 14, the water content of the calcium carbonate powder was 0.1%.

Examples 17 to 20

In contrast to example 16, the isocyanates are different and are specified in Table 2.

TABLE 2 examples 16-20(kg)

	Example 16	Example 17	Example 18	Example 19	Example 20
						Diphenylmethane diisocyanate	200	0	120	130	137.5
Polyphenylene polymethylene polyisocyanate	0	200	80	70	62.5

Examples 21 to 24

The differences of the catalyst from example 19 are shown in Table 3.

TABLE 3 catalyst proportioning Table (kg) in examples 21-24

	Example 21	Example 22	Example 23	Example 24
					Triethylamine	0.2	0.6	1.0	0.1
Dibutyl diisoTin octylate	1.2	0.8	0.3	1.3

Comparative example

Comparative example 1

Unlike example 3, the raw material contained no calcium carbonate powder.

Comparative example 2

Unlike example 3, the calcium carbonate powder had an average particle size of 0.2 μm, a powder weight ratio of the calcium carbonate powder having a particle size of less than 2 μm was 50%, and a powder weight ratio of the calcium carbonate powder having a particle size of less than 5 μm was 80%.

Comparative example 3

Unlike example 3, the calcium carbonate powder had an average particle size of 25 μm, a powder weight ratio of 50% for calcium carbonate powder having a particle size of less than 2 μm and a powder weight ratio of 80% for calcium carbonate powder having a particle size of less than 5 μm.

Comparative example 4

Unlike example 3, the degree of activation of the calcium carbonate powder was 60%.

Comparative example 5

In contrast to example 3, the starting material contained no diethyl N, N-2-hydroxyethylaminomethylphosphonate.

Performance test

Detection method

The heat insulating properties of the rigid polyurethane foam heat insulating materials in examples 1 to 24 and comparative examples 1 to 5 were measured at 25 ℃ according to the thermal conductivity test method for plastics, the thermal protection plate method (GB/T3399-1982).

The density of the rigid polyurethane foam thermal insulation materials in examples 1-24 and comparative examples 1-5 was measured according to the determination of apparent density of foam and rubber (GB/T6343-2009).

The compressive strength of the polyurethane rigid foam insulation materials of examples 1-24 and comparative examples 1-5 was measured according to "determination of compression Properties of rigid foams" (GB/T8813-2020).

The flame retardant properties of the rigid polyurethane foam thermal insulation materials in examples 1 to 24 and comparative examples 1 to 5 were measured according to the determination of the combustion behavior by the oxygen index method for plastics (GB/T2406.1-2008).

The results of the performance measurements are shown in Table 4.

TABLE 4 Performance test results

As can be seen by combining examples 1-24 and comparative examples 1-5 and table 4, the thermal conductivity of the thermal insulation materials prepared in examples 1-24 is lower than that of comparative examples 1-5, and the density, compressive strength and limiting oxygen index are all higher than that of comparative examples 1-5, which shows that the thermal insulation materials prepared in the application have better thermal insulation performance, strength and flame retardant property.

Combining the example 3 and the comparative example 1, and combining the table 4, it can be seen that the thermal insulation performance, strength, and flame retardant performance of the thermal insulation material prepared in the example 3 are significantly better than those of the comparative example 1, which indicates that the addition of the calcium carbonate powder in the present application has a significant forward effect on improving the thermal insulation performance, strength, and flame retardant performance of the thermal insulation material, and this is probably because the organic polyurethane material and the inorganic powder are connected together, so that the calcium carbonate powder plays a role of a nucleation point when a cell structure in a polyurethane foaming process is formed, the cell structure is formed with the calcium carbonate powder particles as a center, so that the cell diameter is reduced, the cell density is increased, and the cell wall of the rigid foam material is thickened, thereby improving the compressive strength of the polyurethane rigid foam thermal insulation material, and also improving the thermal insulation performance of the polyurethane rigid foam thermal insulation material.

By combining the examples 3, 9-12 and the comparative examples 2-4 and combining the table 4, it can be seen that the thermal insulation performance, the strength and the flame retardant performance of the thermal insulation material prepared in the example 3 are obviously superior to those of the comparative example 1, the thermal insulation performance, the strength and the flame retardant performance of the thermal insulation materials prepared in the comparative examples 2-4 are greatly different, and the thermal insulation performance, the strength and the flame retardant performance of the thermal insulation materials prepared in the examples 9-12 are also greatly different; this shows that the particle size and the activation degree of the calcium carbonate powder have a large influence on the performance of the thermal insulation material, and a certain matching relationship exists between the particle size and the activation degree, for example, the particle size of the calcium carbonate powder in comparative example 2 is smaller than that in example 3, but the performance of the thermal insulation material in example 3 is still better than that in comparative example 2, and the activation degree of the calcium carbonate powder in example 11 is lower than that in example 9, but the performance of the thermal insulation material in example 11 is still better than that in example 9.

By combining the example 3 and the comparative example 5 and combining the table 4, it can be seen that the thermal insulation performance and the strength of the thermal insulation material in the comparative example 5 are poorer than those of the example 3, but the disadvantages are not obvious, while the flame retardant performance of the thermal insulation material in the comparative example 5 is greatly reduced than that of the example 3, which is probably because the flame retardant performance of the diethyl N, N-2-hydroxyethylaminomethylphosphonate is improved because the flame retardant performance of the thermal insulation material is improved by matching the diethyl N, N-2-hydroxyethylaminomethylphosphonate with calcium carbonate powder, which is used as an auxiliary agent of the diethyl N, N-2-hydroxyethylaminomethylphosphonate.

Combining examples 3 and 6-8, and table 4, it can be seen that the insulation, strength, and flame retardancy of the insulation of examples 6-8 are better than those of example 3, probably because increasing the pressure appropriately facilitates the thorough mixing of the raw materials in the foaming system, thereby improving the performance of the insulation.

Combining example 11 with examples 13-15, and combining table 4, it can be seen that the thermal insulation performance, strength, and flame retardant performance of the thermal insulation materials in examples 13-15 are better than example 11, which may be because the particle size of the calcium carbonate powder is controlled in a smaller range, so that the calcium carbonate powder particles are more uniform, the formed cell structure is more uniform, the compactness and uniformity of the cell structure are improved, and the cell walls of the hard foam material are thickened; the reason why the difference between the particle diameters of the powders in example 14 is smaller than that in example 13 is probably because the difference between the particle diameters of the powders in example 14 is smaller than that in example 13, is that the weight ratio of the powders having the particle diameters smaller than 5 μm in example 13 is 99%, and the weight ratio of the powders having the particle diameters smaller than 5 μm in example 14 is only 95%.

The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.