CN113480923A

CN113480923A - Ultra-soft polyurethane and preparation method and application thereof

Info

Publication number: CN113480923A
Application number: CN202110841063.XA
Authority: CN
Inventors: 胡群建
Original assignee: Ningbo Hengda Protective Articles Co ltd
Current assignee: Ningbo Hengda Protective Articles Co ltd
Priority date: 2021-07-24
Filing date: 2021-07-24
Publication date: 2021-10-08

Abstract

The application relates to the technical field of polyurethane composite coatings, in particular to ultra-soft polyurethane and a preparation method and application thereof. The super-soft polyurethane is prepared from the following raw materials in percentage by weight: 40-80% of polyester polyol; 20-60% of polyurethane resin; 0-20% of additive, and the solid content of the polyurethane resin is between 20-40%. The preparation method of the super-soft polyurethane comprises the following steps: (1) preparing an ultra-soft polyurethane base liquid; (2) preparing the ultra-soft polyurethane. The super-soft polyurethane and the preparation method have the effect of improving the comfort degree of operators when wearing gloves.

Description

Ultra-soft polyurethane and preparation method and application thereof

Technical Field

The application relates to the technical field of polyurethane composite coatings, in particular to ultra-soft polyurethane and a preparation method and application thereof.

Background

The polyurethane coating is a common coating with the yield second to that of alkyd resin paint, acrylic resin paint and phenolic resin paint, and can be divided into single-component polyurethane coating and double-component polyurethane coating, wherein the single-component polyurethane coating has excellent elasticity and water resistance and is further widely applied to the fields of water resistance, life protection and the like; the two-component polyurethane coating has excellent hardness and wear resistance, and is further widely applied to the fields of industrial protection, automobile coatings and the like.

In the related art, the traditional one-component polyurethane coating is usually prepared by taking a prepolymer containing isocyanate groups, which is obtained by addition polymerization of polycyanate ester and polyether polyol, as a main coating and adding conventional functional additives such as a flame retardant, a reinforcing agent, a catalyst, an antioxidant and the like according to actual requirements.

In view of the above-mentioned related arts, the inventors have considered that, although the above-mentioned one-component polyurethane coating has excellent water resistance and heat stability, the softness thereof is relatively poor, so that there is a drawback that when the above-mentioned one-component polyurethane coating is applied to protective articles such as gloves, operators feel uncomfortable when wearing the gloves.

Disclosure of Invention

In order to improve the comfort degree of operators when wearing gloves, the application provides the ultra-soft polyurethane and the preparation method and application thereof.

In a first aspect, the present application provides an ultra-soft polyurethane, which adopts the following technical scheme:

the super-soft polyurethane is prepared from the following raw materials in percentage by weight: 40-80% of polyester polyol; 20-60% of polyurethane resin; 0-20% of additive, and the solid content of the polyurethane resin is between 20-40%.

By adopting the technical scheme, when the polyester polyol and the polyurethane resin are mixed under the specific gravity, the softness and the ductility of the polyurethane resin can be effectively improved by the polyester polyol, and the comfort degree of operators when wearing gloves is indirectly improved.

In addition, the solid content of the polyurethane resin is between 20 and 40 percent, so that the polyurethane resin can be stably bonded on the surface of the glove, the flexibility and the extensibility of the super-soft polyurethane resin can be effectively improved, and the comfort degree of operators when wearing the glove is further improved.

Preferably, the feed is prepared from the following raw materials in percentage by weight: 55-65% of polyester polyol; 35-45% of polyurethane resin; 0-10% of additive.

By adopting the technical scheme, when the polyester polyol and the polyurethane resin are mixed under the specific gravity, the softness and the ductility of the polyurethane resin can be further effectively improved by the polyester polyol, and the comfort degree of operators when wearing gloves is further improved.

Preferably, the polyurethane resin is one of polyurethane resin XCW-50GH, polyurethane resin XCW-35GL, polyurethane resin WPC694, polyurethane resin WPC696 and polyurethane resin W-6923B.

Preferably, the polyurethane resin is a polyurethane resin XCW-35 GL.

By adopting the technical scheme, when the polyurethane resin is polyurethane resin XCW-35GL, the polyurethane resin XCW-35GL can be more stably adhered to the surface of the glove, and meanwhile, the softness and the ductility of the super-soft polyurethane can be improved, so that the comfort degree of an operator when the operator wears the glove is effectively improved.

Preferably, the polyester polyol is one of polyester polyol W-103, polyester polyol W104, polyester polyol XCP-35EBD, polyester polyol XCP-SP60NL and polyester polyol MP-3000.

Preferably, the polyester polyol is polyester polyol W-103.

By adopting the technical scheme, when the polyester polyol is polyester polyol W-103, the ductility and the flexibility of the polyurethane resin can be more effectively improved by the polyester polyol W-103, and the comfort degree of operators wearing gloves is further improved.

Preferably, the additive is one or a mixture of more of polypropylene glycol, dioctyl phthalate and environment-friendly plasticizer PU-80.

Preferably, the additive is a mixture of an environment-friendly plasticizer PU-80 and dioctyl phthalate, and the ratio of the environment-friendly plasticizer PU-80 to the dioctyl phthalate is 1 (6-10).

By adopting the technical scheme, when the additive adopts the mixture of the environment-friendly plasticizer PU-80 and the dioctyl phthalate dibutyl ester, the additive effectively improves the ductility and the flexibility of the polyurethane resin through the self plasticizing effect, and the comfort degree of operators when wearing the gloves is further improved.

In addition, because the price of the environment-friendly plasticizer PU-80 is relatively low, when the additive is a mixture of the environment-friendly plasticizer PU-80 and dioctyl dibutyl ester with the specific gravity, the mixed additive can effectively reduce the cost for preparing the super-soft polyurethane while not reducing the softness and the extensibility of the polyurethane resin.

In a second aspect, the present application provides a method for preparing an ultra-soft polyurethane, which adopts the following technical scheme:

a preparation method of ultra-soft polyurethane comprises the following steps:

(1) mixing polyester polyol and polyurethane resin for 8-12h to obtain ultra-soft polyurethane base liquid;

(2) heating the ultra-soft polyurethane base liquid to 75-85 ℃, then keeping the temperature for 0.5-1.5h, then adding the additive, cooling to 65-75 ℃, stirring for 0.5-1.5h, and finally cooling to obtain the ultra-soft polyurethane.

Through adopting above-mentioned technical scheme, stir when polyester polybasic acid and polyurethane resin when above-mentioned stirring time, polyester polyol can carry out intensive mixing with polyurethane resin, and then effectively improves polyester polyol to polyurethane resin's compliance and malleable promotion effect, the comfort level when indirectly improving operating personnel and dressing gloves.

In addition, when the super-soft polyurethane base liquid is subjected to the heating and cooling operation, the polyester polyol, the polyurethane resin and the additive can be mixed more fully, so that the flexibility and the ductility of the super-soft polyurethane are further improved, and the comfort degree of operators wearing gloves is further improved.

In a third aspect, the present application provides an application of an ultra-soft polyurethane, which adopts the following technical scheme:

the application of the super-soft polyurethane is to coat the super-soft polyurethane on the surfaces of protective articles such as protective gloves, protective raincoats, protective headgear and the like.

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

1. because this application adopts polyurethane resin XCW-35GL as polyurethane resin, so polyurethane resin can be when more stable bonding in the surface of gloves, can also improve the compliance and the ductility of super gentle polyurethane, and then obtained the effect of the comfort level when improving operating personnel and dress gloves.

2. In the present application, polyester polyol W-103 is preferably used as the polyester polyol, so that the polyester polyol can more effectively improve the ductility and flexibility of the polyurethane resin, and the effect of improving the comfort of the operator wearing the glove is obtained.

3. According to the method, through the long-time stirring, the improvement effect of the softness and the ductility of the polyester polyol to the polyurethane resin is effectively improved, and therefore the effect of improving the comfort degree of operators when wearing gloves is obtained.

Drawings

FIG. 1 is a flow diagram of a process for preparing an ultra-soft polyurethane provided herein.

Detailed Description

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

Raw materials

The raw material components in the present application are shown in table 1.

TABLE 1 sources of the Material Components

Examples

Example 1

An ultra-soft polyurethane is prepared by the following steps:

(1) mixing 60 wt% of polyester polyol W-103 with 40 wt% of polyurethane resin XCW-50GH (solid content of 30%) at a temperature of 25 ℃ and a stirring speed of 200r/min for 10h to obtain an ultra-soft polyurethane base liquid;

(2) heating the ultra-soft polyurethane base liquid to 80 ℃, keeping the temperature for 1h, mixing the ultra-soft polyurethane base liquid at the temperature of 70 ℃ at the stirring speed of 400r/min for 1h, cooling the ultra-soft polyurethane base liquid to 25 ℃, and finally obtaining the ultra-soft polyurethane.

Examples 2 to 5

The differences from example 1 are that the specific gravities of the polyester polyol W-103 and the polyurethane resin XCW-50GH (solid content: 30%) in examples 2-9 are different, as shown in Table 2.

TABLE 2 compositions of raw materials and specific gravities thereof in examples 1 to 5 (wt%)

Composition of raw materials	Polyester polyol W-103	Polyurethane resin XCW-50GH
			Example 1	60	40
Example 2	80	20
			Example 3	40	60
Example 4	55	45
			Example 5	65	35

Example 6

The difference from example 1 is that the polyurethane resin XCW-50GH (solid content 30%) was replaced with the polyurethane resin XCW-35GL (solid content 30%) of the same specific gravity.

Example 7

The difference from example 1 is that the polyurethane resin XCW-50GH (solid content 30%) was replaced with a polyurethane resin WPC694 (solid content 30%) of the same specific gravity.

Example 8

The difference from example 1 is that the polyurethane resin XCW-50GH (solid content 30%) was replaced with the polyurethane resin WPC696 (solid content 40%) of the same specific gravity.

Example 9

The difference from example 1 is that the polyurethane resin XCW-50GH (solid content: 30%) was replaced with the polyurethane resin W-6923B (solid content: 20%) having the same specific gravity.

Example 10

The difference from example 1 is that the polyurethane resin XCW-50GH (solid content of 30%) was replaced with a mixture of the polyurethane resin XCW-50GH (solid content of 30%) and the polyurethane resin XCW-35GL (solid content of 30%) having the same specific gravity, and the ratio of the polyurethane resin XCW-50GH (solid content of 30%) to the polyurethane resin XCW-35GL (solid content of 30%) was 1: 10.

Example 11

The difference from example 1 is that polyester polyol W-103 is replaced with polyester polyol W104 of the same specific gravity.

Example 12

The difference from example 1 is that polyester polyol W-103 is replaced by polyester polyol XCP-35EBD of the same specific gravity.

Example 13

The difference from example 1 is that polyester polyol W-103 is replaced with polyester polyol XCP-SP60NL of the same specific gravity.

Example 14

The difference from example 1 is that polyester polyol W-103 is replaced with polyester polyol MP-3000 of the same specific gravity.

Example 15

The difference from example 1 is that the polyester polyol W-103 was replaced with a mixture of polyester polyol W-103 and polyester polyol W104 of the same specific gravity, and the specific gravity of the polyester polyol W-103 and polyester polyol W104 was 10: 1.

Example 16

An ultra-soft polyurethane is prepared by the following steps:

(1) mixing 48% of polyester polyol W-103 with 32% of polyurethane resin XCW-50GH (solid content is 30%) at a temperature of 25 ℃ and a stirring speed of 200r/min for 10h to obtain an ultra-soft polyurethane base liquid;

(2) heating the ultra-soft polyurethane base liquid to 80 ℃ and keeping the temperature constant for 1h, then adding 20% of polypropylene glycol PPG2000, mixing at the temperature of 70 ℃ at the stirring speed of 400r/min for 1h, and then cooling to 25 ℃ to finally obtain the ultra-soft polyurethane.

Examples 17 to 19

The differences from example 16 are that the specific gravities of the polyester polyol W-103, the polyurethane resin XCW-50GH (30% solid content), and the polypropylene glycol PPG2000 in examples 16 to 19 are different, as shown in Table 3.

TABLE 3 compositions of raw materials and specific gravities thereof in examples 16 to 19 (wt%)

Composition of raw materials	Polyester polyol W-103	Polyurethane resin XCW-50GH	Polypropylene glycol PPG2000
				Example 16	48	32	20
Example 17	51	34	15
				Example 18	54	36	10
Example 19	57	38	5

Example 20

The difference from example 19 is that polypropylene glycol PPG2000 was replaced with dioctyl phthalate CX1082 of the same specific gravity.

Example 21

The difference from example 19 is that the polypropylene glycol PPG2000 was replaced with the environmentally friendly plasticizer PU-80 having the same specific gravity.

Example 22

The difference from example 19 is that polypropylene glycol PPG2000 was replaced with a mixture of dioctyl phthalate CX1082 and environmentally friendly plasticizer PU-80 having the same specific gravity, and the weight ratio of dioctyl phthalate CX1082 to environmentally friendly plasticizer PU-80 was 10: 1.

Example 23

The difference from example 22 is that the weight ratio of dioctyl phthalate CX1082 to the environmentally friendly plasticizer PU-80 is 6: 1.

Example 24

The difference from example 22 is that the weight ratio of dioctyl phthalate CX1082 to the environmentally friendly plasticizer PU-80 is 8: 1.

Example 25

The difference from example 1 is that in (1), the mixing time was 8 hours.

Example 26

The difference from example 1 is that in (1), the mixing time is 12 h.

Example 27

An ultra-soft polyurethane is prepared by the following steps:

(1) 60% of polyester polyol W-103 and 40% of polyurethane resin XCW-50GH (solid content: 30%) are mixed at a temperature of 25 ℃ for 12h with a stirring speed of 200r/min, and then ultra-soft polyurethane is obtained.

Comparative example

Comparative example 1

A preparation method of polyurethane comprises the following steps:

s1, 25 wt% MH-polycyanate was reacted with 75 wt% polyether EP-330NG at a temperature of 85 ℃ for 3h, followed by obtaining the polyurethane.

Comparative example 2

The difference from example 1 is that the polyester polyol W-103 is replaced with the polyurethane resin XCW-50GH (solid content of 30%) of the same specific gravity, i.e., the ultra-soft polyurethane of comparative example 2 is prepared only from the polyurethane resin XCW-50GH (solid content of 30%).

Comparative example 3

The difference from example 19 is that polypropylene glycol PPG2000 was replaced with a polyurethane soft foam catalyst RP-205 of the same specific gravity.

Performance test

Detection method

Three samples were taken from each of examples 1-27 and comparative examples 1-3, and then uniformly coated on the surface of the same glove batch, followed by curing under the same environment and time, and finally examined as follows and averaged.

Test one, ductility test

With reference to GB/T6344-1996, determination of tensile strength and elongation at break of flexible foam Polymer, the ultra-soft polyurethane on the above samples was peeled off and subjected to tensile testing and elongation at break was calculated.

Test two, softness test

The ultra-soft polyurethane on the above samples was peeled and stretched to 100% and the 100% modulus was calculated, according to the method of GB/T6344-1996 "determination of tensile Strength and elongation at Break of Flexible foam Polymer Material".

Test III, adhesion Strength test

The above samples and gloves were subjected to a peel test by twenty testers, and the adhesion firmness to the above samples was represented by "Sa" according to a few majority-compliant principles.

Sa0, difficult to peel;

sa 1: can be partially peeled off;

sa 2: easy to be stripped.

And (3) detection results: the results of the tests of examples 1 to 27 and comparative examples 1 to 3 are shown in tables 4 and 5.

TABLE 4 TABLE of test results of examples 1 to 27 and comparative examples 1 to 3

TABLE 5 TABLE of examination results of example 1 and examples 6 to 10

Example 1

Example 6

Example 7

Example 8

Example 9

Example 10

Degree of adhesion

Sa0

Sa1

Sa0

Sa2

Sa0

When example 1 and comparative examples 1 to 2 are combined and table 4 is combined, the elongation at break of example 1 is obviously improved, and the 100% modulus of example 1 is also obviously reduced, compared with comparative examples 1 and 2, thereby showing that the polyester polyol W-103 has the effect of improving the ductility and flexibility of the polyurethane resin XCW-6650D.

As can be seen from examples 1 to 5 and Table 4, the elongation at break of examples 2 to 5 is reduced compared to example 1, and the 100% modulus of examples 2 to 5 is also improved, which shows that the effect of improving the ductility and flexibility of the polyester polyol W-103 to the polyurethane resin XCW-6650D is the best in the specific gravity of example 1 between the polyester polyol W-103 and the polyurethane resin XCW-6650D.

It can be seen from the combination of example 1 and examples 6 to 9 and table 4 that, compared to example 6, the elongation at break of example 1 and examples 7 to 9 was significantly reduced, and the 100% modulus of example 1 and examples 7 to 9 was also significantly improved, wherein the change width of the elongation at break and the 100% modulus of example 8 was the largest, which indicates that the elongation and flexibility of super soft polyurethane were the best when polyurethane resin XCW-35GL was used, and the elongation and flexibility of super soft polyurethane were the worst when polyurethane resin WPC696 was used.

It can be seen from the combination of examples 1, 6 and 10 and table 4 that the elongation at break of example 10 is still significantly reduced and the 100% modulus of example 10 is also significantly improved compared to example 6, which shows that even a small amount of polyurethane resin XCW-6650D is added to polyurethane resin XCW-35GL, there is a certain negative effect on the extensibility and flexibility of the ultra-soft polyurethane, i.e., the extensibility and flexibility of the ultra-soft polyurethane is improved most when polyurethane resin XCW-35GL is used alone.

In addition, it can be seen from the combination of example 1 and examples 6 to 10 and table 5 that the bonding effect is excellent in all of examples 1, 6, 8 and 10, while the bonding effect is slightly poor in example 7 and the bonding effect is the worst in example 9, which means that the bonding effect is worse as the solid content is higher.

Combining example 1 and examples 11-14 with table 4, it can be seen that the elongation at break of examples 11-14 is significantly reduced, and the 100% modulus of examples 11-14 is also significantly improved, compared to example 1, wherein the elongation at break and 100% modulus of example 14 change to the greatest extent, thus demonstrating that when polyester polyol is polyester polyol W-103, the ductility and flexibility of ultra-soft polyurethane are the best, and when polyester polyol is polyester polyol MP-3000, the ductility and flexibility of ultra-soft polyurethane are the worst.

As can be seen from the combination of example 1, example 11 and example 15 and table 4, the elongation at break of example 15 is still significantly reduced, and the 100% modulus of example 15 is also significantly improved, compared to example 1, which shows that even a small amount of polyester polyol W-104 is added to polyester polyol W-103, the polyurethane composition has a certain negative effect on the extensibility and flexibility of the ultra-soft polyurethane, that is, when polyester polyol W-103 is used alone, the polyurethane composition has the best effect on enhancing the extensibility and flexibility of the ultra-soft polyurethane.

As can be seen by combining example 1, example 16 and comparative example 3, and combining table 4, compared to example 1, the elongation at break and 100% modulus of comparative example 1 are not significantly changed, but the elongation at break and 100% modulus of example 16 are significantly reduced, thereby indicating that the polypropylene glycol PPG2000 has a significant improvement effect on the softness of the ultra-soft polyurethane, and the polypropylene glycol PPG2000 has a certain negative effect on the extensibility of the ultra-soft polyurethane.

It can be seen from the combination of examples 16-19 and table 4 that, although the 100% modulus of examples 17-19 is not greatly changed, the elongation at break of examples 17-19 is significantly improved compared to example 16, wherein the improvement effect of the elongation at break of example 19 is the best, even better than that of example 1, thereby demonstrating that the polypropylene glycol PPG2000 has the best improvement effect on the ductility and softness of the super-soft polyurethane at the specific gravity of example 19.

As can be seen by combining examples 19 to 21 and table 4, the elongation at break of examples 19 and 21 is significantly reduced, and the 100% modulus of examples 19 and 21 is also significantly improved, compared to example 20, wherein the changes of the elongation at break and the 100% modulus of example 21 are the largest. It is shown that when dioctyl phthalate CX1082 is used as an additive, the super soft polyurethane is most excellent in ductility and flexibility, and when PU-80, which is an environmentally friendly plasticizer, is used as an additive, the super soft polyurethane is least excellent in ductility and flexibility.

As can be seen by combining examples 20-24 with Table 4, the elongation at break and 100% modulus of example 22 are not significantly changed relative to example 20, thus indicating that dioctyl phthalate CX1082 can be used in combination with environmentally friendly plasticizer PU-80, and the cost of environmentally friendly plasticizer PU-80 is lower, so that example 22 is better than example 20.

In addition, compared with the example 22, the elongation at break of the example 23 is obviously reduced, the 100% modulus of the example 23 is obviously improved, the elongation at break of the example 24 is slightly reduced, and the 100% modulus of the example 24 is only slightly improved, thereby showing that under the specific gravity of the example 24, the dioctyl phthalate CX1082 and the environment-friendly plasticizer PU-80 can improve the extensibility and the flexibility of the super-soft polyurethane and effectively reduce the cost of the super-soft polyurethane.

It can be seen from the combination of examples 1, 25 and 26 and table 4 that the elongation at break of example 25 is slightly reduced, the 100% modulus of example 25 is improved, and the elongation at break and 100% modulus of example 26 are not changed, compared to example 1, which shows that the mixing time has a certain effect on the extensibility and flexibility of the super soft polyurethane, and the extensibility and flexibility of the super soft polyurethane are relatively better in the mixing time of example 1.

As can be seen from the combination of example 1 and example 27 and table 4, the elongation at break of example 27 is slightly decreased and the 100% modulus of example 27 is improved as compared with example 1, and thus, the temperature increase and decrease operation has a certain effect of improving the stretchability and flexibility of the super soft polyurethane.

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.

Claims

1. The super-soft polyurethane is characterized by being prepared from the following raw materials in percentage by weight: 40-80% of polyester polyol; 20-60% of polyurethane resin; 0-20% of additive, and the solid content of the polyurethane resin is between 20-40%.

2. An ultra-soft polyurethane according to claim 1, wherein: the material is prepared from the following raw materials in percentage by weight: 55-65% of polyester polyol; 35-45% of polyurethane resin; 0-10% of additive.

3. An ultra-soft polyurethane according to claim 1 or 2, wherein: the polyurethane resin is one of polyurethane resin XCW-50GH, polyurethane resin XCW-35GL, polyurethane resin WPC694, polyurethane resin WPC696 and polyurethane resin W-6923B.

4. An ultra-soft polyurethane according to claim 3, wherein: the polyurethane resin is polyurethane resin XCW-35 GL.

5. An ultra-soft polyurethane according to claim 1 or 2, wherein: the polyester polyol is one of polyester polyol W-103, polyester polyol W104, polyester polyol XCP-35EBD, polyester polyol XCP-SP60NL and polyester polyol MP-3000.

6. An ultra-soft polyurethane according to claim 5, wherein: the polyester polyol is polyester polyol W-103.

7. An ultra-soft polyurethane according to claim 1 or 2, wherein: the additive is one or a mixture of more of polypropylene glycol, dioctyl phthalate and an environment-friendly plasticizer PU-80.

8. An ultra-soft polyurethane according to claim 7, wherein: the additive is a mixture of an environment-friendly plasticizer PU-80 and dioctyl phthalate, and the weight ratio of the environment-friendly plasticizer PU-80 to the dioctyl phthalate is 1 (6-10).

9. A method for preparing an ultra-soft polyurethane according to any one of claims 1 to 8, comprising the steps of:

10. Use of an ultra-soft polyurethane according to any one of claims 1 to 8, wherein the ultra-soft polyurethane is applied to the surface of protective gloves, protective raincoats and protective headgear.