CN112932010A

CN112932010A - Women's shoes with anti-cracking vamps and preparation method thereof

Info

Publication number: CN112932010A
Application number: CN202110233805.0A
Authority: CN
Inventors: 陈志凤; 孙立程
Original assignee: Wenzhou Meilianmei Shoes Co ltd
Current assignee: Wenzhou Meilianmei Shoes Co ltd
Priority date: 2021-03-03
Filing date: 2021-03-03
Publication date: 2021-06-11
Anticipated expiration: 2041-03-03
Also published as: CN112932010B

Abstract

The application relates to the field of shoes and discloses a woman's shoe with anti-cracking vamp and a preparation method thereof. The utility model provides a woman's shoe with prevent vamp that ftractures, includes vamp and sole, and the lower surface of vamp is glued a flax fiber layer, and the upper surface of vamp coats and is coated with coating agent, and coating agent includes the raw materials of following parts by weight: 40-50 parts of polybutylene terephthalate; 5-8 parts of benzenedicarboxamide; 3-4 parts of dicyclopentadiene; 1-2 parts of a crosslinking agent; the preparation method comprises the following steps: s1, preparing a coating agent; s2, coating the surface of the vamp; s3, forming the women's shoes; this application has the advantage: the benzene dicarboxyl phenylene diamine and dicyclopentadiene are crosslinked to form a crosslinked network, and then the crosslinked network is blended with linear polybutylene terephthalate, so that the polybutylene terephthalate randomly penetrates through the crosslinked network, a compact and loose alternate two-phase network structure can be formed, the uniformity of the cured network is damaged, the stress dispersion is facilitated, the toughening effect can be achieved, and the anti-cracking performance of the vamp is improved.

Description

Women's shoes with anti-cracking vamps and preparation method thereof

Technical Field

The application relates to the field of shoes, in particular to a women's shoe with an anti-cracking vamp and a preparation method thereof.

Background

The shoes are a necessary daily article in daily life; the prior shoe upper is made of PU material.

At present, the patent of bulletin number CN205682576U discloses a shoes, including sole, vamp and upper of a shoe, sole, vamp and upper of a shoe integrated into one piece, a plurality of holes of vamp and sole junction evenly distributed, the vamp instep is equipped with a plurality of trompils, sole inner bottom palm is equipped with a plurality of stripes and a plurality of protruding grain of massage, sole inner bottom heel is equipped with a plurality of small openings, sole, vamp and upper of a shoe all adopt scattered electric material PVC or PU expanded material.

The above prior art solutions have the following drawbacks: in the process of wearing shoes, the upper is directly exposed to the external environment, exposed to sunlight for a long time, and squeezed by the motion of the foot, so that the upper is easily cracked, and thus, the improvement is still needed.

Disclosure of Invention

In order to reduce the condition of vamp fracture, this application provides a woman's shoe with prevent vamp that ftractures and preparation method thereof.

First aspect, the application provides a woman's shoe with prevent vamp that ftractures adopts following technical scheme:

the women's shoes with prevent vamp that ftractures, including vamp and sole, the lower surface of vamp is glued and is had a flax fiber layer, the upper surface of vamp coats and is coated with coating agent, coating agent includes the following parts by weight's raw materials:

40-50 parts of polybutylene terephthalate;

5-8 parts of benzenedicarboxamide;

3-4 parts of dicyclopentadiene;

1-2 parts of a cross-linking agent.

By adopting the technical scheme, the phenylene terephthalamide and the dicyclopentadiene are crosslinked under the action of the crosslinking agent to form a crosslinked network, and then are blended with the linear polybutylene terephthalate to ensure that the polybutylene terephthalate randomly penetrates through the crosslinked network, so that a compact and loose alternate two-phase network structure can be formed, the uniformity of the cured network is damaged, the stress dispersion is facilitated, the toughening effect can be achieved, and the cracking resistance of the vamp is improved.

Preferably: the raw materials also comprise 2-3 parts of polyether-ether-ketone by weight.

By adopting the technical scheme, the polyether-ether-ketone has higher mechanical property, and the toughness of the coating agent can be effectively improved by mixing the polyether-ether-ketone with high molecular weight and the polybutylene terephthalate, so that the cracking resistance of the vamp can be improved.

Preferably: the raw material also comprises 1-2 parts of 1-octene according to parts by weight.

By adopting the technical scheme, the 1-octene is added, and the active alkenyl contained in the 1-octene reacts with the active carbonyl contained in the polyether-ether-ketone to form a block, so that the toughness of the coating agent is improved, the yield deformation capacity of the vamp can be improved, and the aim of improving the anti-cracking performance is fulfilled.

Preferably: the raw materials also comprise 4-5 parts of 1, 2-glycol by weight.

By adopting the technical scheme, firstly, the polyether-ether-ketone and the 1, 2-glycol are mixed, and bond breaking can occur to obtain chain breaking with active groups, so that the reaction of forming blocks by the polyether-ether-ketone and the 1-octene is easier to carry out, and the toughness of the coating agent is improved; the residual 1, 2-glycol can also be used as a solvent to improve the dispersibility of the components of the coating agent.

Preferably: the raw material also comprises 1-2 parts of nano alumina by weight.

By adopting the technical scheme, the nano aluminum oxide is dispersed in the coating agent component, so that an obvious toughening effect is generated.

Preferably: the raw materials also comprise 2 to 3 parts of glycerin monostearate and 0.6 to 0.8 part of tert-butylamine by weight.

By adopting the technical scheme, the nano-alumina and the glycerin monostearate are uniformly mixed, so that inorganic nano-alumina particles can be uniformly and individually dispersed in the coating agent component, and good interface bonding is formed, so that stress can be better transferred to the nano-alumina, and a relatively obvious toughening effect is obtained; tert-butylamine with steric hindrance is further mixed, so that the agglomeration of nano aluminum oxide can be effectively avoided, and the improvement of the dispersibility is facilitated.

Preferably: the cross-linking agent is hexamethylene diamine dihydrazide.

In a second aspect, the application provides a preparation method of women's shoes with prevent vamp that ftractures, adopts following technical scheme:

a preparation method of women's shoes with anti-cracking vamps comprises the following steps:

s1, preparing a coating agent; mixing benzenedicarboxyl phenylenediamine, dicyclopentadiene and a crosslinking agent, heating to 50-60 ℃, and stirring for 0.5-1 h; adding polybutylene terephthalate, and continuously stirring for 30-40min to obtain a coating agent;

s2, coating the surface of the vamp; coating the coating agent prepared in the step S1 on the upper surface of the vamp with the lower surface adhered with the linen fiber layer, drying, continuously coating, and repeating for 2-3 times;

s3, forming the women's shoes; cut into the shape of required woman 'S shoe with the vamp of S2, then will cut fashioned vamp and sole bonding fixed, the design is finalized and stereotyped in the final arrangement, obtains the finished product woman' S shoe.

Preferably: in S1, the method further includes:

mixing 2-3 parts of polyether-ether-ketone and 4-5 parts of 1, 2-glycol, stirring for 20-25min, then adding 1-2 parts of 1-octene, heating to 40-50 ℃, and stirring for 30-40min to obtain a block compound;

1-2 parts of nano alumina, 2-3 parts of glyceryl monostearate and 0.6-0.8 part of tert-butylamine are blended, and are treated by ultrasonic waves with the ultrasonic power of 100W and the frequency of 20-30kHz for 1-1.5h to obtain a nano mixture;

mixing 5-8 parts of benzenedicarboxamide, 3-4 parts of dicyclopentadiene and 1-2 parts of cross-linking agent, heating to 50-60 ℃, and stirring for 0.5-1 h; adding 40-50 parts of polybutylene terephthalate, and continuously stirring for 30-40 min; then adding the block compound, and stirring for 15-20 min; and finally, adding the nano mixture, and stirring for 1-2h to obtain the coating agent.

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

1. according to the method, phenylene terephthalamide and dicyclopentadiene are crosslinked under the action of a crosslinking agent to form a crosslinked network, and then are blended with linear polybutylene terephthalate to ensure that the polybutylene terephthalate randomly penetrates into the crosslinked network, so that a compact, loose and alternate two-phase network structure can be formed, the uniformity of the cured network is damaged, stress dispersion is facilitated, a toughening effect can be achieved, and the anti-cracking performance of the vamp is improved;

2. polyetheretherketone with high mechanical properties is preferably used in this application; the 1-octene containing active alkenyl and the active carbonyl in the polyether-ether-ketone react to form a block, so that the toughness of the coating agent is improved, the toughness of the coating agent is effectively improved, and the cracking resistance of the vamp is improved;

3. according to the application, the nano-alumina and the glyceryl monostearate are uniformly mixed, so that inorganic nano-alumina particles can be uniformly and individually dispersed in the coating agent component, and good interface bonding is formed, so that stress can be better transferred to the nano-alumina, and a relatively obvious toughening effect is obtained; tert-butylamine with steric hindrance is further mixed, so that the agglomeration of nano aluminum oxide can be effectively avoided, and the improvement of the dispersibility is facilitated.

Detailed Description

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

In the present application, polybutylene terephthalate is purchased from chemical Limited, Wande Hubei; phenylene terephthalamide; dicyclopentadiene is purchased from Nantong Runfeng petrochemical company Limited, the product grade is first grade, and the model is industrial grade; polyetheretherketone was purchased from Shannan, Shuiban plastics, trade name 1; the nano alumina is purchased from Shanghai Yixin chemical company, Inc.; the glyceryl monostearate is purchased from Jiuxing chemical products, Inc. of Hebei, and the total monoglyceride content is more than or equal to 99.2%.

The raw materials used in the following embodiments may be those conventionally commercially available unless otherwise specified; those who do not specify the conditions are performed according to the conventional conditions or the conditions recommended by the manufacturer.

Examples

Example 1

The application discloses woman's shoe with prevent vamp that ftractures, including vamp and sole, the lower surface bonding of vamp has a flax fiber layer, and the upper surface coating of vamp has coating agent, and coating agent includes following raw materials: polybutylene terephthalate, phenylene terephthalamide, dicyclopentadiene and a crosslinking agent, wherein the crosslinking agent is hexamethylene diamine dihydrazide, and the content of each component is shown in the following table 1.

The preparation method of the women's shoes with the anti-cracking vamps comprises the following steps:

s1, preparing a coating agent; mixing benzenedicarboxamide, dicyclopentadiene and a crosslinking agent, heating to 50 ℃, and stirring for 0.5 h; adding polybutylene terephthalate, and continuously stirring for 30min to obtain a coating agent;

s2, coating the surface of the vamp; coating the coating agent prepared in the step S1 on the upper surface of the vamp with the lower surface adhered with the linen fiber layer, drying, continuously coating, and repeating for 2 times;

Example 2

s1, preparing a coating agent; mixing benzenedicarboxamide, dicyclopentadiene and a crosslinking agent, heating to 60 ℃, and stirring for 1 h; adding polybutylene terephthalate, and continuously stirring for 40min to obtain a coating agent;

s2, coating the surface of the vamp; coating the coating agent prepared in the step S1 on the upper surface of the vamp with the lower surface adhered with the linen fiber layer, drying, continuously coating, and repeating for 3 times;

Example 3

s1, preparing a coating agent; mixing benzenedicarboxamide, dicyclopentadiene and a crosslinking agent, heating to 55 ℃, and stirring for 0.8 h; adding polybutylene terephthalate, and continuously stirring for 35min to obtain a coating agent;

Example 4

The difference with embodiment 1 lies in that, this application discloses a woman's shoe with prevent vamp that ftractures, including vamp and sole, the lower surface of vamp is glued there is a flax fiber layer, and the upper surface coating of vamp has coating agent, and coating agent includes following raw materials: polybutylene terephthalate, phenylene terephthalamide, dicyclopentadiene, a cross-linking agent, polyether ether ketone, 1, 2-glycol, 1-octene, nano-alumina, glycerol monostearate and tert-butylamine, wherein the cross-linking agent is hexamethylene diamine dihydrazide, and the content of each component is shown in the following table 1.

In a method for preparing women' S shoes with crack-resistant uppers, the preparation of the S1 coating agent comprises the following steps:

mixing polyether-ether-ketone and 1, 2-glycol, stirring for 20min, then adding 1-octene, heating to 40 ℃, and stirring for 30min to obtain a block compound;

blending nano aluminum oxide, glyceryl monostearate and tert-butylamine, and treating for 1h by ultrasonic waves with the ultrasonic power of 100W and the frequency of 20kHz to obtain a nano mixture;

mixing benzenedicarboxamide, dicyclopentadiene and a crosslinking agent, heating to 50 ℃, and stirring for 0.5 h; adding polybutylene terephthalate, and continuously stirring for 30 min; then adding a block compound, and stirring for 15 min; and finally, adding the nano mixture, and stirring for 1h to obtain the coating agent.

Example 5

mixing polyether-ether-ketone and 1, 2-glycol, stirring for 25min, then adding 1-octene, heating to 50 ℃, and stirring for 40min to obtain a block compound;

blending nano aluminum oxide, glyceryl monostearate and tert-butylamine, and treating for 1.5h by ultrasonic waves with the ultrasonic power of 110W and the frequency of 30kHz to obtain a nano mixture;

mixing benzenedicarboxamide, dicyclopentadiene and a crosslinking agent, heating to 60 ℃, and stirring for 1 h; adding polybutylene terephthalate, and stirring for 40 min; then adding the block compound, and stirring for 20 min; and finally, adding the nano mixture, and stirring for 2 hours to obtain the coating agent.

Example 6

mixing polyether-ether-ketone and 1, 2-glycol, stirring for 23min, then adding 1-octene, heating to 45 ℃, and stirring for 35min to obtain a block compound;

blending nano aluminum oxide, glyceryl monostearate and tert-butylamine, and treating for 1.2h by ultrasonic waves with the ultrasonic power of 105W and the frequency of 25kHz to obtain a nano mixture;

mixing benzenedicarboxamide, dicyclopentadiene and a crosslinking agent, heating to 55 ℃, and stirring for 0.8 h; adding polybutylene terephthalate, and continuously stirring for 35 min; then adding a block compound, and stirring for 18 min; finally, adding the nano mixture, and stirring for 1.5h to obtain the coating agent.

Example 7

The difference from example 1 is that the raw material of the coating agent further includes polyether ether ketone, and the contents of the respective components are shown in table 2 below.

In a method for preparing women' S shoes with crack-resistant uppers, the preparation of the S1 coating agent comprises the following steps: mixing benzenedicarboxamide, dicyclopentadiene and a crosslinking agent, heating to 50 ℃, and stirring for 0.5 h; adding polybutylene terephthalate, and continuously stirring for 30 min; and then adding polyether-ether-ketone, and stirring for 1h to obtain the coating agent.

Example 8

The difference from example 7 is that the raw material of the coating agent further includes 1-octene, and the contents of the respective components are shown in table 2 below.

In a method for preparing women' S shoes with crack-resistant uppers, the preparation of the S1 coating agent comprises the following steps: mixing polyether-ether-ketone and 1-octene, heating to 40 ℃, and stirring for 30min to obtain a block compound;

mixing benzenedicarboxamide, dicyclopentadiene and a crosslinking agent, heating to 50 ℃, and stirring for 0.5 h; adding polybutylene terephthalate, and continuously stirring for 30 min; then, the block compound was added and stirred for 1 hour to obtain a coating agent.

Example 9

The difference from example 8 is that the raw material of the coating agent further includes 1, 2-ethanediol, and the contents of the components are shown in table 2 below.

Example 10

The difference from example 7 is that polyether ether ketone was replaced with polyether ether and the contents of the respective components are shown in table 2 below.

Example 11

The difference from example 8 is that 1-octene is replaced by n-butane and the content of each component is shown in table 2 below.

Example 12

The difference from example 9 is that 1, 2-ethanediol was replaced by ethane and the amounts of the components are given in table 2 below.

Example 13

The difference from example 1 is that the raw material of the coating agent further includes nano alumina, and the contents of the components are shown in table 2 below.

In a method for preparing women' S shoes with crack-resistant uppers, the preparation of the S1 coating agent comprises the following steps: mixing benzenedicarboxamide, dicyclopentadiene and a crosslinking agent, heating to 50 ℃, and stirring for 0.5 h; adding polybutylene terephthalate, and continuously stirring for 30 min; and finally adding nano aluminum oxide, and stirring for 1h to obtain the coating agent.

Example 14

The difference from example 13 is that the raw materials of the coating agent further include glyceryl monostearate and t-butylamine, and the contents of the respective components are shown in table 2 below.

In a method for preparing women' S shoes with crack-resistant uppers, the preparation of the S1 coating agent comprises the following steps: blending the glyceryl monostearate and the tert-butylamine, and treating for 1h by ultrasonic waves with the ultrasonic power of 100W and the frequency of 20kHz to obtain a dispersed mixture;

mixing benzenedicarboxamide, dicyclopentadiene and a crosslinking agent, heating to 50 ℃, and stirring for 0.5 h; adding polybutylene terephthalate, and continuously stirring for 30 min; finally, the dispersing mixture is added and stirred for 1h to obtain the coating agent.

Example 15

The difference from example 14 is that glyceryl monostearate was replaced with laureth, and the contents of the respective components are shown in Table 2 below.

Example 16

The difference from example 14 is that tert-butylamine was replaced with methylamine, and the contents of each component are shown in table 2 below.

Comparative example

Comparative example 1

The difference from example 1 is that the upper surface of the upper is not coated with a coating agent.

Comparative example 2

The difference from example 1 is that polybutylene terephthalate is replaced with polytetrafluoroethylene, and the contents of the components are shown in table 1 below.

Comparative example 3

The difference from example 1 is that benzenedicarboxamide was replaced with aniline, and the contents of the respective components are shown in table 1 below.

Comparative example 4

The difference from example 1 is that dicyclopentadiene is replaced with cyclopentane and the component contents are shown in table 1 below.

Comparative example 5

The difference from example 1 is that the crosslinking agent was replaced with carbodiimide and the contents of the respective components are shown in table 1 below.

TABLE 1 component content tables of examples 1 to 6 and comparative examples 2 to 5

	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6	Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5
											Polybutylene terephthalate/polytetrafluoroethylene	40	50	45	40	50	45	40	40	40	40
Benzenedicarboxamides/anilines	5	8	7	5	8	7	5	5	5	5
											Dicyclopentadiene/cyclopentane	3	4	3.5	3	4	3.5	3	3	3	3
Crosslinking agent	1	2	1.5	1	2	1.5	1	1	1	1
											Polyether ether ketone	/	/	/	2	3	2.5	/	/	/	/
1, 2-ethanediol	/	/	/	4	5	4.5	/	/	/	/
											1-octene	/	/	/	1	2	1.5	/	/	/	/
Nano alumina	/	/	/	1	2	1.5	/	/	/	/
											Glyceryl monostearate	/	/	/	2	3	2.5	/	/	/	/
Tert-butylamine	/	/	/	0.6	0.8	0.7	/	/	/	/

TABLE 2 ingredient content tables for examples 7-16

	Example 7	Example 8	Example 9	Example 10	Example 11	Example 12	Example 13	Example 14	Example 15	Example 16
											Polybutylene terephthalate	40	40	40	40	40	40	40	40	40	40
Benzenedicarboxamide	5	5	5	5	5	5	5	5	5	5
											Dicyclopentadiene	3	3	3	3	3	3	3	3	3	3
Crosslinking agent	1	1	1	1	1	1	1	1	1	1
											PolyetherEther-ketone/polyether	2	2	2	2	2	2	/	/	/	/
1, 2-ethanediol/ethane	/	/	4	/	/	4	/	/	/	/
											1-octene/n-butane	/	1	1	/	1	1	/	/	/	/
Nano alumina	/	/	/	/	/	/	1	1	1	1
											Glyceryl monostearate/laureth	/	/	/	/	/	/	/	2	2	2
Tert-butylamine/methylamine	/	/	/	/	/	/	/	0.6	0.6	0.6

Performance test

(1) Testing the toughness; the tensile strength and the elongation at break are used for representing the toughness, vamp sample strips with the length of 5cm and the thickness of 2mm are prepared according to the preparation methods of the examples and the comparative examples, the tensile property is tested by referring to a GB/T1040-1992 method, the tensile speed is 50mm/min, the larger the tensile strength and the elongation at break, the better the toughness and the better the anti-cracking performance; the test results are shown in table 3 below.

TABLE 3 table of results of performance test of each example and comparative example

	Tensile strength/MPa	Elongation at break/%
			Example 1	50	100
Example 2	55	116
			Example 3	53	114
Example 4	58	121
			Example 5	62	126
Example 6	60	124
			Example 7	52	113
Example 8	55	117
			Example 9	57	119
Example 10	50	100
			Example 11	50	99
Example 12	55	117
			Example 13	53	114
Example 14	55	117
			Example 15	53	114
Example 16	53	114
			Comparative example 1	37	78
Comparative example 2	46	95
			Comparative example 3	48	97
Comparative example 4	48	97
			Comparative example 5	49	99

In summary, the following conclusions can be drawn:

1. according to the embodiment 1 and the embodiments 7 to 12 and the combination of the embodiment and the table 3, a certain synergistic effect is achieved between the polyether ether ketone and the 1-octene, and when the 1, 2-glycol reacts with the polyether ether ketone and is further mixed with the 1-octene, the toughening effect of the coating agent is improved, so that the effect of better improving the toughness of the shoe upper is achieved, and the anti-cracking performance of the shoe upper can be improved.

2. As can be seen from example 1 and examples 13-16 in combination with table 3, the addition of nano alumina has a toughening effect; on the basis, glycerin monostearate and tert-butylamine are added, so that the toughening effect of the coating agent can be further improved, and the function of improving the cracking resistance of the vamp is achieved.

3. As can be seen from example 1 and comparative example 1 in combination with Table 3, the shoe uppers treated with the coating agent of the present application are more flexible and have better resistance to cracking.

4. According to the example 1 and the comparative examples 2 to 4 and the combination of the components shown in the table 3, the polybutylene terephthalate, the phenylene terephthalamide and the dicyclopentadiene are added together, so that the toughening effect of the coating agent can be effectively improved, and the cracking resistance of the shoe upper can be improved.

5. As can be seen from example 1 and comparative example 5 in combination with Table 3, the use of hexamethylenediamine dihydrazide as a crosslinking agent for the reaction of phenylenediamide and dicyclopentadiene in the present application improves the crack resistance of the upper to some extent, probably because the use of this crosslinking agent improves the toughness of the coating agent to some extent.

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 to the present embodiment as necessary without inventive contribution after reading the present specification, but all are protected by patent law within the scope of the claims of the present application.

Claims

1. The utility model provides a woman's shoe with prevent vamp that ftractures, includes vamp and sole, the lower surface bonding of vamp has a flax fiber layer, its characterized in that: the upper surface of the vamp is coated with a coating agent, and the coating agent comprises the following raw materials in parts by weight:

40-50 parts of polybutylene terephthalate;

5-8 parts of benzenedicarboxamide;

3-4 parts of dicyclopentadiene;

1-2 parts of a cross-linking agent.

2. The women's shoe with crack-resistant upper according to claim 1, characterized in that: the raw materials also comprise 2-3 parts of polyether-ether-ketone by weight.

3. The woman's shoe with the anti-crack upper according to claim 2, characterized in that: the raw material also comprises 1-2 parts of 1-octene according to parts by weight.

4. The woman's shoe with the anti-crack upper according to claim 3, characterized in that: the raw materials also comprise 4-5 parts of 1, 2-glycol by weight.

5. The women's shoe with crack-resistant upper according to claim 1, characterized in that: the raw material also comprises 1-2 parts of nano alumina by weight.

6. The woman's shoe with the anti-crack upper according to claim 5, characterized in that: the raw materials also comprise 2 to 3 parts of glycerin monostearate and 0.6 to 0.8 part of tert-butylamine by weight.

7. The woman's shoe having an anti-splitting upper according to claim 1, wherein said cross-linking agent is hexamethylene diamine dihydrazide.

8. The method for preparing women's shoes with anti-cracking uppers according to claim 1, characterized in that it comprises the following steps:

9. The method for preparing women's shoes with anti-cracking uppers, according to claim 8, characterized in that: in S1, the method further includes: