CN1006800B - Hot melt adhesives for stretched shoe front tip and the preparation thereof - Google Patents
Hot melt adhesives for stretched shoe front tip and the preparation thereofInfo
- Publication number
- CN1006800B CN1006800B CN 87101456 CN87101456A CN1006800B CN 1006800 B CN1006800 B CN 1006800B CN 87101456 CN87101456 CN 87101456 CN 87101456 A CN87101456 A CN 87101456A CN 1006800 B CN1006800 B CN 1006800B
- Authority
- CN
- China
- Prior art keywords
- adhesive
- hot melting
- polypropylene
- consumption
- weight part
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Abstract
The present invention belongs to a hot melting adhesive for preparing stretched shoe front tips by polypropylene and a preparation method thereof. Isotactic polypropylene is used as the base material of the adhesive. Organic peroxide, a nucleating agent and antioxidant are added to form the hot melting adhesive. All main raw materials and all auxiliary raw materials are industrial grades without a special requirement. The hot melting adhesive has the advantages of simple equipment of production technology and no need of the technologies of the purification, the condensation, the copolymerization, etc. of the raw materials; the cost of the hot melting adhesive is only 1/4 of the cost of a stretched polyester last adhesive. The hot melting adhesive is suitable for variousinsole materials, such as leather, paper boards, regenerated leather, etc., and has good adhesive force.
Description
The invention belongs to degradation of polypropylene and develop hot melt adhesives for stretched shoe front tip.
The employed shoe last or hat block hot melt adhesive that stretches tight of prior art (comprising the stretch tight paracone and the flank that stretches tight) all is to be that base-material is (referring to " polyester hot-melt adhesive summary ", the technology final report of units such as Shanghai Leather Shoes Factory, the Yellow River, Shanghai Leather Shoes Factory, in May, 1975 with polyester and polymeric amide; " footwear are summed up with polymeric amide hot-melt adhesive technology ", the technology final report of units such as Shanghai Leather Shoes Factory, Shanghai light industry institute, in April, 1975).Polyester, polymeric amide can satisfy the requirement of specific equipment fully on use properties as the shoe last or hat block hot melt adhesive that stretches tight, but, the complex manufacturing of these two kinds of tackiness agents singly be that polymerization stage just needs about four hours, and production technique is to adopt the gap production method basically.There is certain restriction in these two kinds of binder materials sources in addition, and price is also higher, and especially at home, these two problems are more outstanding.
GB1407356 patent documentation and for example, using aliphatic superoxide is 2.5-dimethyl-2.5 tertiary butyl peroxidation hexane and 2.5-dimethyl-2.5 tertiary butyl peroxidation hexin-3, makes degradation of polypropylene.Can only improve polyacrylic processing characteristics with this superoxide, be applicable to crowded film, common plastics processings such as spinning, its flowing property is still low, do not have the possibility of making the hot melt adhesive base-material, in particular for the leather shoes shoe last or hat block hot melt adhesive that stretches tight, requiring has higher curing speed and thermostability, then more is not suitable for.
The present invention seeks to the weak point that exists at prior art, by degradation of polypropylene and add necessary additive, make a kind of performance and polyester, polymeric amide is suitable, and the low novel paracone hotmelt that stretches tight of cost.
Technical solution of the present invention is to use polypropylene with the isotactic structure base-material as hotmelt, adds organo-peroxide, nucleator (Nucleation agent) and oxidation inhibitor and constitutes hotmelt.
Because the molecular weight of commercially available acrylic resin is higher, generally between 20-40 ten thousand, on the shoe last or hat block working temperature that stretches tight, polyacrylic melt viscosity is quite big, can reach 10
4More than the pool, obviously, this is impossible directly as the hot melt adhesive base-material.Need to add organo-peroxide, make it under appropriate temperature, carry out DeR, obtain low viscosity, perviousness, low-molecular-weight polypropylene that binding property is good.Organo-peroxide as the degradation agents use, comprise dicumyl peroxide (DCP), di-t-butyl peroxide (DTBP), 2.5-dimethyl-2.5 tertiary butyl peroxidation hexane (DMBPH) etc., foul smelling flavor when dicumyl peroxide decomposes, it under the room temperature solid phase prod, be unfavorable for producing, 2.5-dimethyl-2.5 tertiary butyl peroxidation hexane and di-t-butyl peroxide are liquid product, the former has flavor slightly during decomposition, and the latter is tasteless.The decomposition temperature of di-t-butyl peroxide is 193 ℃, the transformation period be 1 minute with polyacrylic to extrude processing temperature quite approaching, help DeR and carry out.The consumption of superoxide depends primarily on the height of polypropylene molecule amount size and DeR temperature, usually the consumption of superoxide is 0.1-3 weight part (is 100 parts in polypropylene weight), be preferably the 0.5-1.5 weight part, the DeR temperature is generally 150-250 ℃, is preferably 175-225 ℃.
Although the polypropylene after the degraded is the isotactic crystallinity polymkeric substance, directly as stretching tight the paracone tackiness agent, its curing speed is lower, does not satisfy production requirement, therefore, also need add nucleator with the raising crystallization velocity, thereby improve curing speed.Nucleator comprises organic and inorganic product, as silicon-dioxide, titanium dioxide, zinc oxide, talcum powder, calcium stearate, Zinic stearas, hexanodioic acid, phenylformic acid, Sodium Benzoate and oxalic acid etc.Produce the foul smell flavor when stretching tight the paracone adhesive melts, the organic acid nucleator that should try one's best and to bring stink.The consumption of nucleator is generally 0.1-5 weight part (is 100 parts in polypropylene weight), is preferably the 0.5-2 weight part.
In order to improve the thermostability of the paracone tackiness agent that stretches tight, also add phenolic antioxidant in the tackiness agent of the present invention, as oxidation inhibitor 2,6,4 and antioxidant 1010.The consumption of oxidation inhibitor is generally the 0.01-0.2 weight part.
Technology of the present invention is extrusion method, and forcing machine is adjustable speed, thermoregulated general type.Its technical process is as follows:
Polypropylene, organo-peroxide, nucleator and oxidation inhibitor are pressed formula rate metering, mix the back and add in the forcing machine, at room temperature use water cooling through adding after hot-extrudable, pelletizing is a finished product.
The embodiment of the invention:
Example 1: 100 parts of polypropylene (MI=1, Singapore Polymer Company produces)
1 part of di-t-butyl peroxide (technical grade)
0.5 part in zinc oxide (technical grade)
0.1 part of antioxidant 1010 (technical grade)
Above-mentioned each component mixed to add model be that SJ-45B(Shanghai forcing machine factory produces) in the forcing machine, in temperature is 200 ℃, extrude under the speed of rotating speed for per minute 30-40 commentaries on classics, at room temperature use water cooling, pelletizing is the finished product paracone hotmelt that stretches tight, and fusing point is 165 ± 2 ℃, and softening temperature is 140 ± 5 ℃, shoe last or hat block operating time of stretching tight is 4-6 second, and the shoe last or hat block service temperature that stretches tight is 220 ℃.
Example 2: 100 parts of polypropylene (MI=13, Yanshan Mountain board 3702)
0.5 part of di-t-butyl peroxide (technical grade)
0.5 part of titanium dioxide (technical grade)
Oxidation inhibitor 2,6,4(technical grade) 0.1 part
Technology, result are with example 1.
Example 3: 100 parts of polypropylene (MI=13, Yanshan Mountain board 3702)
1 part of di-t-butyl peroxide (technical grade)
0.5 part of silicon-dioxide (technical grade)
Oxidation inhibitor 2,6,4(technical grade) 0.1 part
The extrusion reaction temperature is 175 ℃, and all the other are with example 1.
Example 4: 100 parts of polypropylene (MI=1.5, SHELL CANADA company)
1 part of di-t-butyl peroxide (technical grade)
0.2 part of hexanodioic acid (technical grade)
0.1 part of antioxidant 1010 (technical grade)
Technology, result are with example 1.
Example 5: 100 parts of polypropylene (MI=13, Yanshan Mountain board 3702)
1.5 parts of di-t-butyl peroxides (technical grade)
0.4 part of Zinic stearas (technical grade)
0.2 part of calcium stearate (technical grade)
Oxidation inhibitor 2,6,4(technical grade) 0.1 part
Technology, result are with example 3.
The present invention compares with polyester, polyamide PU lasting adhesive, and it is extensive to have raw material sources, and various main and auxiliary raw materials are technical grade, no specific (special) requirements, and production technology, equipment are simple, need not to carry out the operations such as feed purification, polycondensation, copolymerization. The present invention's paracone adhesive proportion little (for 0.91-0.93, polyester is more than 1.1, and polyamide is 0.97) that stretches tight, Unit Weight stretch tight front class adhesive than polyester, the polyamide PU lasting adhesive shoe last or hat block that stretches tight more, and cost only is 1/4th of polyester PU lasting adhesive.
The present invention compares with the GB1407356 patent, and the employing di-t-butyl peroxide is degradation agent, can obtain the degradation product than high fluidity, possesses the condition as PUR. In prescription, also added the nucleator that can improve curing rate, made the PUR that makes to satisfy the requirement of the shoe last or hat block technology that stretches tight.
Adhesive of the present invention is to leather and present employed various interior bottom materials, all has good bonding force such as leather, cardboard, regenerated leather etc., upper of a shoe and the interior end,, bonding destruction all occurred on the interior bottom material, and shear strength is at 5Kg/cm2More than.
Claims (4)
1, a kind of hot melt adhesives for stretched shoe front tip that under heating, makes isotatic polypropylene degraded and make with organo-peroxide, it is characterized in that: with isotatic polypropylene as base-material, superoxide is a di-t-butyl peroxide, when this hotmelt of preparation, in isotatic polypropylene weight is 100 parts, and the di-t-butyl peroxide consumption is the 0.1-3 weight part; The nucleator consumption is the 0.1-5 weight part; The oxidation inhibitor consumption is the 0.01-0.2 weight part.
2, tackiness agent according to claim 1 is characterized in that: in isotatic polypropylene weight is 100 parts, and the better consumption of di-t-butyl peroxide is the 0.5-1.5 weight part; The better consumption of nucleator is the 0.5-2 weight part.
3, tackiness agent according to claim 1 and 2 is characterized in that nucleator is zinc oxide, titanium dioxide, silicon-dioxide, hexanodioic acid, Zinic stearas, calcium stearate.
4, tackiness agent according to claim 1 is characterized in that: making the temperature of reaction of isotatic polypropylene degraded with di-t-butyl peroxide is 150-250 ℃, and better temperature of reaction is 175-225 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87101456 CN1006800B (en) | 1987-11-28 | 1987-11-28 | Hot melt adhesives for stretched shoe front tip and the preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87101456 CN1006800B (en) | 1987-11-28 | 1987-11-28 | Hot melt adhesives for stretched shoe front tip and the preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87101456A CN87101456A (en) | 1988-04-20 |
| CN1006800B true CN1006800B (en) | 1990-02-14 |
Family
ID=4813441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87101456 Expired CN1006800B (en) | 1987-11-28 | 1987-11-28 | Hot melt adhesives for stretched shoe front tip and the preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1006800B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101153095B (en) * | 2006-09-29 | 2010-05-12 | 中国石油化工股份有限公司 | Chemical degradation method of polypropylene |
| WO2012068573A2 (en) * | 2010-11-19 | 2012-05-24 | Henkel Corporation | Adhesive compositions and use thereof |
| CN105585969B (en) * | 2016-02-18 | 2018-06-01 | 东莞广泽汽车饰件有限公司 | A kind of fixing means on leather cladding border |
-
1987
- 1987-11-28 CN CN 87101456 patent/CN1006800B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN87101456A (en) | 1988-04-20 |
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