WO2017194033A1

WO2017194033A1 - Polyurethane molded plastic mattress composition and preparation method therefor

Info

Publication number: WO2017194033A1
Application number: PCT/CN2017/091014
Authority: WO
Inventors: 徐军; 孙清峰; 殷玉鹏; 郭勇生; 代金辉; 梁玲; 陈伟
Original assignee: 山东一诺威聚氨酯股份有限公司
Priority date: 2016-07-21
Filing date: 2017-06-30
Publication date: 2017-11-16
Also published as: CN106117488A; CN106117488B; RU2705946C1

Abstract

Provided are a polyurethane molded plastic mattress composition and a preparation method therefor. The composition consists of an A component and a B component, raw materials of the A component being: a highly active polyether polyol, a polymer polyol, a macromolecular chain extender, a foam stabilizer, a foaming agent, a catalyst and a flame retardant, raw materials of the B component being: a polyether polyol, an isocyanate and a storage stabilizer. The composition has excellent fluidity and is suitable for preparing large polyurethane molded plastic mattresses having complex molds. The preparation method is simple and easy to implement.

Description

Polyurethane molded mattress composition and preparation method thereof

Technical field

The invention belongs to the field of polyurethane synthesis, and in particular relates to a polyurethane molded mattress composition and a preparation method thereof.

Background technique

The mattresses commonly used today are spring mattresses and polyurethane foam mattresses. However, after a long time of use, the spring mattress is prone to loss of elasticity, hard deformation, and poor air permeability. Polyurethane foam mattress is a mainstream trend nowadays. The traditional molding method is cutting method, that is, the whole foam is cut according to the required shape, then bonded to the skeleton with adhesive, and then wrapped with other materials. cover. The use of conventional cutting methods produces scraps, which makes the foam utilization low and costly, and the sponge mattress is not strong enough to be deformed for a long time and loses its elasticity.

The patent of CN 1107582C, entitled "Mattress and its production method and special mold", illustrates the advantages of using a molding method to prepare a polyurethane mattress, but the specific chemical composition of the polyurethane composition is not clearly defined. set forth.

Summary of the invention

In view of the deficiencies of the prior art, the object of the present invention is to provide a polyurethane molded mattress composition which has excellent fluidity and is suitable for preparing a polyurethane molded mattress having a large size and a complicated mold; the present invention also provides a preparation method thereof .

One aspect of the present invention provides a polyurethane molded mattress composition comprising an A component and a B component, wherein

Component A, in parts by weight, includes:

Component B, in parts by weight, includes:

Polyether polyol 20-60 parts;

Isocyanate 40-80 parts;

The storage stabilizer accounts for 0.001% of the total weight of the B component.

Wherein, the high-activity polyether polyol is a polyether polyol having a primary hydroxyl group content of ≥70%.

Preferably, the weight ratio of the A component to the B component is A: B = 100: 30 to 60.

Preferably, the high-activity polyether polyol is one or more of glycerol, triethanolamine or trimethylolpropane, and the primary hydroxyl group content is ≥70%, and the number average molecular weight is 4000. ～8000, a polyoxypropylene triol terminated with ethylene oxide. The high-activity polyether polyol is used in the polyurethane composition of the invention, and the prepared polyurethane molded mattress product has the advantages of high activity and short demolding time, and can effectively improve the load-bearing property and resilience of the polyurethane product. In order to achieve the above object, the content of the high-activity polyether polyol in the component A is limited to a range of 50 to 85 parts, but it is understood that those skilled in the art can reasonably perform the above range according to actual needs. The adjustment may be, for example, 55 parts, 60 parts, 65 parts, 75 parts, 80 parts, or the like.

Preferably, the polymer polyol is one or both of MD30-15 or MD22-40. MD30-15 and MD22-40 are manufactured by Shell Chemical Company. Polymer polyols are organically filled polyether polyols used to produce high load or high modulus soft or semi-rigid polyurethane foam articles. By adding such an organic filled polyether, it is possible to produce a foam having a low density and a high load-bearing property, which achieves both hardness and material. In order to maximize the effect of the above polymer polyol, the content thereof is limited to the range of 10 to 50 parts, but it can be understood that those skilled in the art can appropriately adjust within the above range according to actual needs, for example, It is 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, and the like.

Preferably, the macromolecular chain extender is prepared by adding polymerization reaction of diethanolamine or triethanolamine as a starting agent and adding propylene oxide, and the molecular weight thereof is 200-600. The chain extender is a small molecule alcohol or amine which can react with a functional group on a polymer chain to expand a molecular chain and increase the molecular weight. The present application successfully applies a macromolecular chain extender to a polyurethane composition for molding a mattress, which has excellent fluidity and is suitable for preparing a polyurethane molded mattress of a large size and a complicated mold. The content of the macromolecular chain extender in the component A is limited to the range of 0.1 to 1.5 parts, but it is understood that those skilled in the art can carry out the above range according to the degree of molecular chain expansion and the complexity of the mold. A reasonable selection may be, for example, 0.5 parts, 0.8 parts, 1 part, or the like.

Preferably, the catalyst is one or both of MP601 or MP602. MP601 and MP602 are produced by American Gas Chemical Company. The catalyst can shorten the reaction time, increase the production efficiency, selectively promote the positive reaction, suppress the side reaction, and achieve the desired balance between the foaming reaction and the gel reaction. The amount of the above catalyst added is not too much, and only needs to be catalyzed. For example, in the range of 0.1-2.5 parts mentioned above, 0.2 parts, 0.5 parts, 0.8 parts, 1 part, 1.5 parts may be taken according to the actual reaction requirements. , 2 copies, etc.

Preferably, the foam stabilizer is one or more of SI 1103, SI 1304 or SI 1306. Stable foam The agent, also known as a foam stabilizer, functions to emulsify the foam material, stabilize the foam, and regulate the cells. The foam stabilizer is preferably a polysiloxane-oxyalkylene block copolymer, more preferably one or more of SI 1103, SI 1304 or SI 1306. SI 1103, SI 1304 and SI 1306 are produced by the American Gas Chemical Company. The content of the foam stabilizer is limited to 0.1-1.5 parts, and can be reasonably selected according to actual needs, for example, 0.2 parts, 0.5 parts, 0.8 parts, 1 part, and the like.

Preferably, the foaming agent is water, and the foaming agent expands, foams and solidifies the viscoelastic foam material to obtain a polyurethane foam. It adopts full water foaming, is non-toxic and environmentally friendly, does not damage the ozone layer, and has zero ozone depletion potential (ODP). Therefore, the prepared polyurethane composition for molded mattress is an environment-friendly material. The content of the foaming agent is limited to 2.5-4.5 parts, and can be reasonably selected according to the actual degree of foaming, for example, 2.8 parts, 3 parts, 3.5 parts, 4 parts, and the like.

Preferably, the flame retardant is one or both of the oligomeric phosphate flame retardant Fyrol PNX or Fyrol PNX-S. After the flame retardant is added, the flame retardancy of the polyurethane product can be improved. Fyrol PNX and Fyrol PNX-S are manufactured by Akzo Nobel of the United States. The present invention limits the content of the flame retardant to be in the range of 0.1-5.0 parts, and can be selected according to the requirements of the flame retardant effect of the product, for example, 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5. 4 parts, 4.5 parts, etc.

Preferably, the polyether polyol is one or more of ZS-1618A, ZS-1820 or ZS-1808. Polyether polyols are not only easy to obtain raw materials, low in cost, but also have good performance in polyurethane foams, and are the largest polyol raw materials used in polyurethane foams. ZS-1618A, ZS-1820 and ZS-1808 are produced by Jiangsu Zhongshan Chemical Co., Ltd. The present invention limits the content of the polyether polyol in the B component to a range of 20-60 parts, but those skilled in the art can reasonably select within the above range according to actual needs, for example, 25 parts, 30 parts. 35, 40, 45, 50, 55, etc.

Preferably, the isocyanate is one or more of Lupranate M, Lupranate LP30, Lupranate MM103C or Lupranate M20S. Isocyanate is an important basic raw material for the synthesis of polyurethane. It has a wide range of sources, good economics and excellent physical properties. Lupranate M, Lupranate LP30, Lupranate MM103C and Lupranate M20S are manufactured by BASF, Germany. The present invention limits the isocyanate content to a range of 40-80 parts, but those skilled in the art can reasonably select within the above range according to actual needs, for example, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70, 75, etc.

Preferably, the storage stabilizer is phosphoric acid or benzoyl chloride. The storage stabilizer prevents the side reaction of the isocyanate and improves the storage stability of the product. The above storage stabilizer can achieve the purpose of improving storage stability by adding a small amount. The storage stabilizer in the present invention is 0.001% of the total weight of the component B, but it can be understood that those skilled in the art can according to actual needs. The adjustment is reasonably carried out in the vicinity of the above content.

According to another aspect of the present invention, there is provided a preparation method of a polyurethane molded mattress composition according to any of the above aspects. The law includes the following steps:

(1) A component: firstly weigh the high-activity polyether polyol and polymer polyol into the reaction kettle, then add the accurate molecular chain extender, catalyst, foaming agent and foam stabilizer. , flame retardant, physical stirring at room temperature for 3-4 hours;

(2) Component B: The weighed polyether polyol is put into the reaction kettle at normal temperature and stirred. After rising to 80 ° C ~ 100 ° C, dehydration and degassing, and then cooling to 10 ~ 40 ° C, adding accurate storage stability. The reagent is added to the isocyanate, and the temperature is raised to 80-85 ° C for 2 to 3 hours, and after sampling and testing, the temperature is lowered to 10 to 40 ° C;

The above sampling test is qualified to have an isocyanate content of between 20 and 35%;

The A and B components are mechanically or manually mixed at a weight ratio of A:B=100:30-60 at room temperature, and uniformly mixed to obtain the polyurethane molded mattress composition;

The above polyurethane molded mattress composition is injected into an aluminum molded mattress mold, and can be processed into a polyurethane molded mattress product after being subjected to mold removal at room temperature for 2 to 10 minutes.

In other words, at room temperature, the A and B components are mechanically or hand-mixed according to the weight ratio of A:B=100:30-60, and then injected into the aluminum molded mattress mold, after 2 to 10 minutes of normal temperature. The mold can be processed into a product by curing.

The above-mentioned normal temperature is 30 to 70 ° C, and may be within the above range according to actual needs. For example, it may be 35 ° C, 40 ° C, 45 ° C, 50 ° C, 55 ° C, 60 ° C, 65 ° C, and the like.

Wherein, the dehydration and degassing is vacuuming to a vacuum degree ≤ -0.098 MPa, and a moisture content ≤ 0.05%.

The above percentage percentages are all by weight.

In summary, the present invention has the following advantages:

(1) The components A and B are stored in a liquid state at normal temperature, which saves energy and reduces cumbersome operations.

(2) It adopts full water foaming in formula design, and its ozone destruction effect ODP value is zero, non-toxic and environmentally friendly, and it is an environment-friendly material.

(3) The macromolecular chain extender has been successfully applied to polyurethane molded mattress compositions, and has excellent fluidity, and is suitable for preparing polyurethane molded mattresses of large size and complicated molds.

(4) The preparation method described is simple and easy to implement.

detailed description

The technical solutions in the embodiments of the present invention are clearly and completely described below. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative efforts are within the scope of the present invention.

The materials used in the following examples are commercially available unless otherwise specified.

The highly reactive polyether polyols and macromolecular chain extenders employed in the following examples were prepared by the methods described in the Summary of the Invention and using conventional procedures.

Example 1

(1) Preparation of component A:

Weighing separately: high-activity polyether polyol 80 kg, polymer polyol MD30-15 20 kg, macromolecular chain extender 1.2 kg, foam stabilizer SI 1103 1.2 kg, water 3.0 kg, catalyst MP601 1.3 kg, flame retardant Fyrol PNX 2.0 kg. Wherein the high-activity polyether polyol is a polyoxypropylene triol with glycerol as a starting agent, a primary hydroxyl group content of 70%, a number average molecular weight of 4000, and an ethylene oxide capping; The chain agent is prepared by adding polymerization reaction of diethanolamine as a starting agent and adding propylene oxide, and has a molecular weight of 200.

The weighed high-activity polyether polyol and polymer polyol are put into the reaction kettle and stirred, and then weighed into the weighed macromolecular chain extender, catalyst, foaming agent, foam stabilizer and flame retardant. Physically stirred at room temperature for 3.0 hours, and packed into a warehouse.

(2) Preparation of component B:

20 kg of polyether polyol ZS-1618A was added to the reaction kettle at room temperature, stirred at 100 ° C, vacuumed (vacuum degree ≤ -0.098 MPa) dehydrated and degassed (moisture content 0.05%), cooled to 10 ° C, added phosphoric acid (accounting for 0.001% of the total weight of the B component), while investing in Lupranate M 80 kg, reacting at 80 ° C for 2.5 hours, after sampling and testing, cooling to 40 ° C, loading into the warehouse.

When used, the A and B components are mechanically mixed at a weight ratio of A:B=100:30 at room temperature and then injected into an aluminum molded mattress mold. After 3 minutes at room temperature, the mold can be processed into a product. .

Example 2

(1) Preparation of component A:

Weighing separately: high-activity polyether polyol 85 kg, polymer polyol MD 30-15 10 kg, polymer polyol MD 22-40 10 kg, macromolecular chain extender 0.6 kg, foam stabilizer SI 1304 0.1 kg 2.5 kg of water, 2.5 kg of catalyst MP601, and 4.0 kg of flame retardant Fyrol PNX. Wherein, the high-activity polyether polyol is a polyoxypropylene triol with triethanolamine as a starting agent, a primary hydroxyl group content of 75%, a number average molecular weight of 5000, and an ethylene oxide capping; The agent is prepared by adding polymerization reaction of triethanolamine as a starting agent and adding propylene oxide, and the molecular weight thereof is 300.

The weighed high-activity polyether polyol and polymer polyol are put into the reaction kettle and stirred, and then weighed into a weighed chain extender, a catalyst, a foaming agent, a foam stabilizer and a flame retardant, respectively, at normal temperature. Physically stirred for 3.5 hours, packed in a bucket.

(2) Preparation of component B:

40 kg of polyether polyol ZS-1820 was added to the reaction kettle at room temperature, stirred at 95 ° C, vacuumed (vacuum degree ≤ -0.098 MPa) dehydrated and degassed (moisture content 0.05%), and cooled to 20 ° C to add phosphoric acid ( 0.001% of the total weight of the B component, while investing 60 kg of Lupranate M, reacting at 82 ° C for 3 hours, after passing the sampling test, cooling to 30 ° C, loading into the warehouse.

When used, the A and B components are mechanically mixed at a weight ratio of A:B=100:45 at room temperature, and then injected into an aluminum molded mattress mold. After 5 minutes at room temperature, the mold can be processed into a product. .

Example 3

(1) Preparation of component A:

Weighing separately: 50 kg of high-activity polyether polyol, MD 22-40 10 kg of polymer polyol, 1.2 kg of macromolecular chain extender, foam stabilizer SI 1306 0.2 kg, foam stabilizer SI 13040.1 kg, water 2.5 kg , catalyst MP602 2.0 kg, catalyst MP601 0.5 kg, flame retardant Fyrol PNX-S 5.0 kg. Wherein the high-activity polyether polyol is a polyoxypropylene triol with trimethylolpropane as a starting agent, a primary hydroxyl group content of 80%, a number average molecular weight of 7000, and an ethylene oxide cap; The molecular chain extender is prepared by adding polymerization reaction of diethanolamine as a starting agent and adding propylene oxide, and has a molecular weight of 500.

The weighed high-activity polyether polyol and polymer polyol are put into the reaction kettle and stirred, and then weighed into a weighed chain extender, a catalyst, a foaming agent, a foam stabilizer and a flame retardant, respectively, at normal temperature. Physically stirred for 4.0 hours, packed in a bucket.

(2) Preparation of component B:

60 kg of polyether polyol ZS-1808 was added to the reaction kettle at room temperature, stirred at 90 ° C, vacuumed (vacuum degree ≤ -0.098 MPa) dehydrated and degassed (moisture content 0.05%), and the temperature was lowered to 30 ° C to add phosphoric acid ( 0.001% of the total weight of the B component, while investing 40 kg of Lupranate M, reacting at 85 ° C for 2.5 hours, after sampling and testing, cooling to 20 ° C, loading into the warehouse.

When used, the A and B components are mechanically mixed to a uniform weight ratio of A:B=100:60 at room temperature, and then injected into an aluminum molded mattress mold. After 8 minutes of normal temperature curing, the mold can be processed into product.

Example 4

(1) Preparation of component A:

Weighing separately: 60 kg of high-activity polyether polyol, 50 kg of polymer polyol MD22-40, 1.5 kg of macromolecular chain extender, foam stabilizer SI 1103 0.2 kg, water 4.5 kg, catalyst MP602 2.2 kg, flame retardant Fyrol PNX-S 1.0 kg, flame retardant Fyrol PNX 1.0 kg. Wherein the high-activity polyether polyol is a polyoxypropylene triol with glycerol as a starting agent, a primary hydroxyl group content of 85%, a number average molecular weight of 8000, and an ethylene oxide capping; The chain agent is prepared by adding polymerization reaction of triethanolamine as a starting agent and adding propylene oxide, and has a molecular weight of 600.

(2) Preparation of component B:

20 kg of polyether polyol ZS-1618A and polyether polyol ZS-1808 15 kg were added to the reaction kettle at room temperature, stirred at 80 ° C, vacuumed (vacuum degree ≤ -0.098 MPa) dehydration and degassing (moisture content 0.05 %), reduce the temperature to 40 ° C to add phosphoric acid (accounting for 0.001% of the total weight of the B component), while investing Lupranate M 25 kg, Lupranate MM103C 20 kg, Lupranate M20S 20 kg, 85 ° C reaction for 2.5 hours, after sampling and testing, cooling Pack to the warehouse at 10 °C.

When used, the A and B components are mechanically mixed to a uniform weight ratio of A:B=100:55 at room temperature, and then injected into an aluminum molded mattress mold. After 8 minutes of normal temperature curing, the mold can be processed into product.

The molded mattress articles prepared in Examples 1-4 and the commercially available molded mattress articles were subjected to performance tests, and the test results are shown in Table 1.

Table 1 Performance Test Results of Molded Mattress Products and Commercial Products Prepared in Examples 1-4

As can be seen from Table 1, the molded mattress products prepared in Examples 1-4 of the present invention have lower density, tensile strength, elongation at break, tearing than the existing commercially available molded mattress products. The crack strength is greatly improved, and the indentation hardness and the ball rebound rate are also improved, indicating that the molded mattress prepared in the embodiment 1-4 of the present invention is not only compared with the existing molded mattress. It is lighter in weight, strong in resistance to deformation, good in elasticity and long in service life.

Claims

A polyurethane molded mattress composition characterized by comprising an A component and a B component, wherein

Component A is in parts by weight:

Component B is in parts by weight:

Polyether polyol 20-60 parts;

Isocyanate 40-80 parts;

The storage stabilizer accounts for 0.001% of the total weight of the B component.
The polyurethane molded mattress composition according to claim 1, wherein the high-activity polyether polyol is one or more of glycerol, triethanolamine or trimethylolpropane. Starting agent, polyoxypropylene triol terminated with ethylene oxide, having a primary hydroxyl group content of ≥70% and a number average molecular weight of 4000 to 8000.
The polyurethane molded mattress composition according to claim 1, wherein said polymer polyol is one or both of MD30-15 or MD22-40.
The polyurethane molded mattress composition according to claim 1, wherein the macromolecular chain extender is prepared by addition polymerization of propylene oxide by using diethanolamine or triethanolamine as a starting agent. Its molecular weight is 200-600.
The polyurethane molded mattress composition according to claim 1, wherein the catalyst is one or two of MP601 or MP602; and the foam stabilizer is one of SI 1103, SI 1304 or SI 1306. Kind or several; the foaming agent is water.
The polyurethane molded mattress composition according to claim 1, wherein the flame retardant is one or both of Fyrol PNX or Fyrol PNX-S.
The polyurethane molded mattress composition according to claim 1, wherein the polyether polyol is one or more of ZS-1618A, ZS-1820 or ZS-1808.
The polyurethane molded mattress composition according to claim 1, wherein the isocyanate is one or more of Lupranate M, Lupranate LP30, Lupranate MM103C or Lupranate M20S; and the storage stabilizer is phosphoric acid or benzene. Formyl chloride.
A method for preparing a polyurethane molded mattress composition according to any one of claims 1-8, comprising the steps of:

(1) A component: firstly weigh the high-activity polyether polyol and polymer polyol into the reaction kettle, then add the accurate molecular chain extender, catalyst, foaming agent and foam stabilizer. , flame retardant, physical stirring at room temperature for 3-4 hours;

(2) Component B: The weighed polyether polyol is put into the reaction kettle at normal temperature and stirred. After rising to 80 ° C ~ 100 ° C, dehydration and degassing, and then cooling to 10 ~ 40 ° C, adding accurate storage stability. The reagent is added to the isocyanate, and the temperature is raised to 80-85 ° C for 2 to 3 hours, and after sampling and testing, the temperature is lowered to 10 to 40 ° C;

At room temperature, the A and B components are mechanically or hand-mixed according to the weight ratio of A:B=100:30-60, and then injected into the aluminum molded mattress mold. After 2 to 10 minutes of curing at room temperature, the mold is removed. Can be processed into products.
The method for preparing a polyurethane molded mattress composition according to claim 9, wherein the dehydration and degassing is vacuuming to a vacuum degree of ≤ -0.098 MPa and a moisture content of ≤ 0.05%.