CN101314655A - Rubber material containing hyperbranched 4A molecular sieve and preparation method thereof - Google Patents
Rubber material containing hyperbranched 4A molecular sieve and preparation method thereof Download PDFInfo
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- CN101314655A CN101314655A CNA2008100403238A CN200810040323A CN101314655A CN 101314655 A CN101314655 A CN 101314655A CN A2008100403238 A CNA2008100403238 A CN A2008100403238A CN 200810040323 A CN200810040323 A CN 200810040323A CN 101314655 A CN101314655 A CN 101314655A
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Abstract
The invention provides a rubber material containing superbranched 4A molecular sieve and the preparation method thereof. The rubber material contains, regarding a rubber matrix with 100 weight parts as a benchmark, 1 to 5 weight parts of superbranched 4A molecular sieve, wherein the superbranched 4A molecular sieve is the resultant of 4A molecular sieve and N,N-dihydroxy-3-aminopropanoate. The rubber material containing superbranched 4A molecular sieve has good mechanical performance and good compatibility with other additives of rubber products, and can meet the requirement for the manufacture process of rubber product.
Description
Technical field
The present invention relates to a kind of rubber composite that contains hyperbranched 4 A molecular sieve and preparation method thereof.
Background technology
The 4A molecular sieve is an artificial lens type silico-aluminate, adsorbs or repel the molecule of different substances according to the size in its crystals hole, thereby is called " molecular sieve " visually.The 4A molecular sieve is by two AlO
4And SiO
4The truncated octahedra that tetra-atomic ring connects is formed, and its 3 D pore canal big hole is separated by the aperture that eight yuan of oxygen rings form, and free diameter is 0.42nm.Molecular sieve structure is special, has absorption, catalytic premium properties.The thermostability height of molecular sieve is able to take 600-700 ℃ high temperature.4A molecular sieve industrial technology maturation, preparation technology is simple, and cost is low, is one of molecular sieve kind of industrial consumption maximum.
The 4A molecular sieve as activity is rigid filled can be to macromolecular material increase-volume reinforcement such as rubber, and vital role is arranged to improving performances such as elastomeric material heatproof combustion resistance, anti-aging and moisture resistance be wear-resisting.Add the 4A molecular sieve in the elastomeric material and can improve its mechanical property, but along with its increase of adding umber, tensile strength descends to some extent, so it is significant that it is carried out surface modification.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of elastomeric material that contains hyperbranched 4 A molecular sieve and preparation method thereof, to overcome the defective that prior art exists.
The said elastomeric material that contains hyperbranched 4 A molecular sieve of the present invention, its component is basic identical with conventional rubber, is benchmark with the rubber matrix of 100 weight parts, contains the hyperbranched 4 A molecular sieve of 1～5 weight part; Said hyperbranched 4 A molecular sieve is 4A molecular sieve and N, the reaction product of N-dihydroxyl-3 amido methyl propionate.
Said hyperbranched 4 A molecular sieve is preparation like this:
1. building-up reactions monomer:
With the mixture of methyl acrylate, diethanolamine and solvent, at N
2Under the atmosphere, 30～50 ℃ of reaction 1～3h remove then and desolvate, and obtain N, N-dihydroxyl-3 amido methyl propionate;
Said solvent is selected from methyl alcohol, ethanol, toluene or dimethylbenzene;
The mol ratio of methyl acrylate and diethanolamine is:
Methyl acrylate: diethanolamine=1: 0.8～1.2, preferred 1: 1;
In the solvent, the content of methyl acrylate is 0.5～1mol/mL;
2. prepare hyperbranched 4 A molecular sieve:
With 4A molecular sieve, step N 1., N-dihydroxyl-3 amido methyl propionate and tosic acid are at N
2Under the protection, 70～90 ℃ were reacted 6～8 hours, and collected hyperbranched 4 A molecular sieve then from reaction product;
The weight part of 4A molecular sieve is 1～5 part, N, and N-dihydroxyl-3 amido methyl propionate weight part is 10～30 parts, the weight part of tosic acid is 0.1～0.3 part;
Preferably, the parts by weight of said each component of elastomeric material that contains hyperbranched 4 A molecular sieve are as follows:
100 parts of rubber matrixs, 2.0～3.0 parts of vulcanizing agents, 0.5～1.0 part of promotor TBTS, 0.5～1.5 part of captax H, 0.5～1.0 part of accelerator NS, 0.6～1.0 part of stearic acid, 1～3 part of nano zine oxide, 0.8～1.2 part of antioxidant D, 20～40 parts of light calcium carbonates, 1～5 part of hyperbranched 4 A molecular sieve.
Said vulcanizing agent is a sulphur;
The chemical name of said promotor TBTS is a TBTM tetrabutyl thiuram monosulfide;
The chemical name of said captax H is 2-mercaptan phenyl and thiazole hexamethylene ammonium salt;
The chemical name of said accelerator NS is a N tert butyl benzothiazole 2 sulfenamide;
Said nano zine oxide and stearic acid are vulcanization leveller, and wherein, the particle diameter of nano zine oxide is 10～70nm;
The chemical name of said antioxidant D is the N-Phenyl beta naphthylamine.
The preparation method of the above-mentioned elastomeric material that contains hyperbranched 4 A molecular sieve comprises the steps:
With rubber matrix, vulcanizing agent, promotor TBTS, captax H, accelerator NS, stearic acid, nano zine oxide, antioxidant D, light calcium carbonate and said hyperbranched 4 A molecular sieve proportionally in mill, under 30～55 ℃ the condition, use conventional methods mixing 0.2～0.5 hour, promptly obtain rubber of the present invention.
The elastomeric material that contains hyperbranched 4 A molecular sieve that the present invention obtained has the good mechanical performance, and with other additive of rubber item good consistency is arranged all, can satisfy the requirement of making in the rubber item process.
Embodiment
Among the embodiment, if no special instructions, be weight part.
Comparative Examples 1
With the 3# smoke sheet rubber: 100 parts; Sulphur: 2.0 parts; Promotor TBTS:0.5 part; Captax H:0.5 part, accelerator NS: 0.5 part, stearic acid: 0.6 part; Nano zine oxide: 1 part; Antioxidant D: 0.8 part; Light calcium carbonate: 40 parts, place mill, mixing 0.5 hour (mixing take traditional method) promptly gets General Purpose Rubber under 30 ℃ temperature.
This elastomeric material is made dumbbell-shaped specimen, and carry out stretching experiment by GB/T1701-2001, gained tensile strength and elongation at break see Table 1.
Comparative Examples 2
With the 3# smoke sheet rubber: 100 parts; Sulphur: 2.5 parts; Promotor TBTS:0.8 part; Captax H:1.0 part; Accelerator NS: 0.8 part, stearic acid: 0.8 part; Nano zine oxide: 2 parts; Antioxidant D: 1.0 parts; Light calcium carbonate: 30 parts, place mill, mixing 0.3 hour (mixing take traditional method) promptly gets General Purpose Rubber under 45 ℃ temperature.
This elastomeric material is made dumbbell-shaped specimen, and carry out stretching experiment by GB/T1701-2001, gained tensile strength and elongation at break see Table 1.
Comparative Examples 3
With the 3# smoke sheet rubber: 100 parts; Sulphur: 3.0 parts; Promotor TBTS:1.0 part; Captax H:1.5 part; Accelerator NS: 1.0 parts, stearic acid: 1.0 parts; Nano zine oxide: 3 parts; Antioxidant D: 1.2 parts; Light calcium carbonate: 20 parts, place mill, mixing 0.2 hour (mixing take traditional method) promptly gets General Purpose Rubber under 55 ℃ temperature.
This elastomeric material is made dumbbell-shaped specimen, and carry out stretching experiment by GB/T1701-2001, gained tensile strength and elongation at break see Table 1.
Embodiment 1
In 250mL four-necked bottle reactor, add the 0.15mol methyl acrylate, 0.15mol diethanolamine and 20mL methyl alcohol, mixture is at logical N
2Be warming up to 30 ℃ under the situation and keep 3h, vacuumize then, obtain a kind of water white transparency oily thing, be i.e. N, N-dihydroxyl-3 amido methyl propionate to remove methyl alcohol.
Take by weighing the N of 1g 4A molecular sieve, 10g, N-dihydroxyl-3 amido methyl propionate and 0.1g tosic acid are in four neck flasks, at N
2Protection under 70 ℃, was stirred 8 hours down, vacuumized then to remove unreacted monomer, obtained containing grafted 4A molecular sieve and the not dope of polymers grafted.
The product methanol wash, centrifugation, throw out repeats above-mentioned steps till detecting less than unreacted matters and polymkeric substance again with centrifugal again behind the solvent wash in washings.Throw out in 40 ℃ of following vacuum-dryings 5 hours, is obtained hyperbranched 4 A molecular sieve.
With the 3# smoke sheet rubber: 100 parts; Sulphur: 2.0 parts; Promotor TBTS:0.5 part; Captax H:0.5 part, accelerator NS: 0.5 part, stearic acid: 0.6 part; Nano zine oxide: 1 part; Antioxidant D: 0.8 part; Hyperbranched 4 A molecular sieve: 1 part; Light calcium carbonate: 40 parts, place mill, mixing 0.5 hour (mixing take traditional method) promptly gets elastomeric material of the present invention under 30 ℃ temperature.
This elastomeric material is made dumbbell-shaped specimen, and carry out stretching experiment by GB/T1701-2001, gained tensile strength and elongation at break see Table 1.
Embodiment 2
In 250mL four-necked bottle reactor, add the 0.20mol methyl acrylate, 0.20mol diethanolamine and 30mL methyl alcohol, mixture is at logical N
2Be warming up to 40 ℃ under the situation and keep 2h, vacuumize then, obtain a kind of water white transparency oily thing, be i.e. N, N-dihydroxyl-3 amido methyl propionate to remove methyl alcohol.
Take by weighing the N of 3g 4A molecular sieve, 20g, N-dihydroxyl-3 amido methyl propionate monomer and 0.2g tosic acid are in four neck flasks, at N
2Under 80 ℃, violent stirring 7 hours vacuumizes then to remove unreacted monomer, obtains containing grafted 4A molecular sieve and the not dope of polymers grafted down in protection.The product methanol wash, centrifugation, throw out repeats above-mentioned steps till detecting less than unreacted matters and polymkeric substance again with centrifugal again behind the solvent wash in washings.Throw out in 50 ℃ of following vacuum-dryings 4 hours, is obtained hyperbranched 4 A molecular sieve.
With the 3# smoke sheet rubber: 100 parts; Sulphur: 2.5 parts; Promotor TBTS:0.8 part; Captax H:1 part; Accelerator NS: 0.8 part, stearic acid: 0.8 part; Nano zine oxide: 2 parts; Antioxidant D: 1.0 parts; Hyperbranched 4 A molecular sieve: 3 parts; Light calcium carbonate: 30 parts, place mill, mixing 0.3 hour (mixing take traditional method) promptly gets elastomeric material of the present invention under 45 ℃ temperature.
This elastomeric material is made dumbbell-shaped specimen, and carry out stretching experiment by GB/T1701-2001, gained tensile strength and elongation at break see Table 1.
Embodiment 3
In 250mL four-necked bottle reactor, add the 0.25mol methyl acrylate, 0.25mol diethanolamine and 40mL methyl alcohol, mixture is at logical N
2Be warming up to 50 ℃ under the situation and keep 1h, vacuumize then, obtain a kind of water white transparency oily thing, be i.e. N, N-dihydroxyl-3 amido methyl propionate to remove methyl alcohol.
Take by weighing the N of 5g 4A molecular sieve, 30g, N-dihydroxyl-3 amido methyl propionate monomer and 0.3g tosic acid are in four neck flasks, at N
2Under 90 ℃, violent stirring 6 hours vacuumizes then to remove unreacted monomer, obtains containing grafted 4A molecular sieve and the not dope of polymers grafted down in protection.The product methanol wash, centrifugation, throw out repeats above-mentioned steps till detecting less than unreacted matters and polymkeric substance again with centrifugal again behind the solvent wash in washings.Throw out in 60 ℃ of following vacuum-dryings 3 hours, is obtained hyperbranched 4 A molecular sieve.
With the 3# smoke sheet rubber: 100 parts; Sulphur: 3.0 parts; Promotor TBTS:1.0 part; Captax H:1.5 part; Accelerator NS: 1.0 parts, stearic acid: 1.0 parts; Nano zine oxide: 3 parts; Antioxidant D: 1.2 parts; Hyperbranched 4 A molecular sieve: 5 parts; Light calcium carbonate: 20 parts, place mill, mixing 0.2 hour (mixing take traditional method) promptly gets elastomeric material of the present invention under 55 ℃ temperature.
This elastomeric material is made dumbbell-shaped specimen, and carry out stretching experiment by GB/T1701-2001, gained tensile strength and elongation at break see Table 1.
Table 1
| Embodiment | Tensile strength (MPa) | Elongation at break (%) |
| Comparative Examples 1 | 18.96 | 600.22 |
| Comparative Examples 2 | 19.05 | 610.78 |
| Comparative Examples 3 | 19.48 | 620.63 |
| Embodiment 1 | 20.98 | 850.46 |
| Embodiment 2 | 21.85 | 1000.25 |
| Embodiment 3 | 22.57 | 1218.94 |
Claims (5)
1. containing the elastomeric material of hyperbranched 4 A molecular sieve, it is characterized in that, is benchmark with the rubber matrix of 100 weight parts, contains the hyperbranched 4 A molecular sieve of 1～5 weight part; Said hyperbranched 4 A molecular sieve is 4A molecular sieve and N, the reaction product of N-dihydroxyl-3 amido methyl propionate.
2. the elastomeric material that contains hyperbranched 4 A molecular sieve according to claim 1 is characterized in that, said hyperbranched 4 A molecular sieve is preparation like this:
1. building-up reactions monomer:
With the mixture of methyl acrylate, diethanolamine and solvent, at N
2Under the atmosphere, 30～50 ℃ of reaction 1～3h remove then and desolvate, and obtain N, N-dihydroxyl-3 amido methyl propionate;
Said solvent is selected from methyl alcohol, ethanol, toluene or dimethylbenzene;
The mol ratio of methyl acrylate and diethanolamine is:
Methyl acrylate: diethanolamine=1: 0.8～1.2, preferred 1: 1;
In the solvent, the content of methyl acrylate is 0.5～1mol/mL;
2. prepare hyperbranched 4 A molecular sieve:
With 4A molecular sieve, step N 1., N-dihydroxyl-3 amido methyl propionate and tosic acid are at N
2Under the protection, 70～90 ℃ were reacted 6～8 hours, and collected hyperbranched 4 A molecular sieve then from reaction product;
The weight part of 4A molecular sieve is 1～5 part, N, and N-dihydroxyl-3 amido methyl propionate weight part is 10～30 parts, the weight part of tosic acid is 0.1～0.3 part.
3. the elastomeric material that contains hyperbranched 4 A molecular sieve according to claim 1 is characterized in that, the parts by weight of said each component of elastomeric material that contains hyperbranched 4 A molecular sieve are as follows:
100 parts of rubber matrixs, 2.0～3.0 parts of vulcanizing agents, 0.5～1.0 part of promotor TBTS, 0.5～1.5 part of captax H, 0.5～1.0 part of accelerator NS, 0.6～1.0 part of stearic acid, 1～3 part of nano zine oxide, 0.8～1.2 part of antioxidant D, 20～40 parts of light calcium carbonates, 1～5 part of hyperbranched 4 A molecular sieve.
4. the elastomeric material that contains hyperbranched 4 A molecular sieve according to claim 3 is characterized in that, said vulcanizing agent is a sulphur;
The chemical name of said promotor TBTS is a TBTM tetrabutyl thiuram monosulfide;
The chemical name of said captax H is 2-mercaptan phenyl and thiazole hexamethylene ammonium salt;
The chemical name of said accelerator NS is a N tert butyl benzothiazole 2 sulfenamide;
The chemical name of said antioxidant D is the N-Phenyl beta naphthylamine.
5. according to each 3 described preparation method who contains the elastomeric material of hyperbranched 4 A molecular sieve of claim 1～4, it is characterized in that, comprise the steps:
With rubber matrix, vulcanizing agent, promotor TBTS, captax H, accelerator NS, stearic acid, nano zine oxide, antioxidant D, light calcium carbonate and said hyperbranched 4 A molecular sieve proportionally in mill, under 30～55 ℃ the condition, mixing 0.2～0.5 hour, i.e. acquisition contains the elastomeric material of hyperbranched 4 A molecular sieve.
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| CNA2008100403238A CN101314655A (en) | 2008-07-08 | 2008-07-08 | Rubber material containing hyperbranched 4A molecular sieve and preparation method thereof |
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| CNA2008100403238A CN101314655A (en) | 2008-07-08 | 2008-07-08 | Rubber material containing hyperbranched 4A molecular sieve and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101899175A (en) * | 2010-06-04 | 2010-12-01 | 上海工程技术大学 | Hyperbranched expandable flame retardant rubber material and preparation method thereof |
| CN101967237A (en) * | 2010-10-28 | 2011-02-09 | 沈阳化工大学 | Preparation method of rubber/mesoporous molecular sieve nanocomposite |
| CN104292525A (en) * | 2014-10-30 | 2015-01-21 | 上海工程技术大学 | Flame retardant rubber and preparation method thereof |
| CN112457539A (en) * | 2020-12-03 | 2021-03-09 | 侯光宇 | Preparation method of high-tensile-strength corrosion-resistant rubber lining material |
-
2008
- 2008-07-08 CN CNA2008100403238A patent/CN101314655A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101899175A (en) * | 2010-06-04 | 2010-12-01 | 上海工程技术大学 | Hyperbranched expandable flame retardant rubber material and preparation method thereof |
| CN101967237A (en) * | 2010-10-28 | 2011-02-09 | 沈阳化工大学 | Preparation method of rubber/mesoporous molecular sieve nanocomposite |
| CN101967237B (en) * | 2010-10-28 | 2012-07-25 | 沈阳化工大学 | Preparation method of rubber/mesoporous molecular sieve nanocomposite |
| CN104292525A (en) * | 2014-10-30 | 2015-01-21 | 上海工程技术大学 | Flame retardant rubber and preparation method thereof |
| CN104292525B (en) * | 2014-10-30 | 2016-04-27 | 上海工程技术大学 | A kind of flame retardant rubber and preparation method thereof |
| CN112457539A (en) * | 2020-12-03 | 2021-03-09 | 侯光宇 | Preparation method of high-tensile-strength corrosion-resistant rubber lining material |
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