CN100586971C - Method for preparing crosslinked carbon dioxide-propylene oxide copolymer - Google Patents
Method for preparing crosslinked carbon dioxide-propylene oxide copolymer Download PDFInfo
- Publication number
- CN100586971C CN100586971C CN200810050978A CN200810050978A CN100586971C CN 100586971 C CN100586971 C CN 100586971C CN 200810050978 A CN200810050978 A CN 200810050978A CN 200810050978 A CN200810050978 A CN 200810050978A CN 100586971 C CN100586971 C CN 100586971C
- Authority
- CN
- China
- Prior art keywords
- carbon dioxide
- weight
- parts
- crosslinked
- epoxy propane
- 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 - Fee Related
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a method for preparing a crosslinked carbon dioxide-propylene oxide copolymer. The method comprises the following steps that: 100 portions of carbon dioxide-propylene oxide copolymer resins, 0.05 to 1 portion of peroxide, 1 to 10 portions of silane coupling agents and 0.01 to 0.3 portion of catalysts are mixed in an internal mixer; the temperature in the internal mixer isbetween 130 and 180 DEG C, and the blending time is between 3 and 10 minutes; and the resins after blending are crosslinked for 4 to 96 hours in hot water at a temperature of between 30 and 90 DEG C after hot press molding at a temperature of 150 DEG C, and then the crosslinked carbon dioxide-propylene oxide copolymer is prepared. The gel content measured is between 15 and 85 percent. The range ofthe mechanical properties is as follows: the tensile strength is between 30 and 45 MPa, and the elongation at break is between 3 and 8 percent. The application scope of the carbon dioxide-propylene oxide copolymer is effectively expanded through crosslinking.
Description
Technical field:
The present invention relates to a kind of preparation method of crosslinked carbon dioxide-epoxy propane copolymer, belong to polymeric material field.
Background technology:
Macromolecular material with characteristics such as its excellent combination property, cheap, easy machine-shapings, extensively is penetrated into each field of the various piece and the people's lives of national economy as a kind of type material, has obtained application more and more widely.Today, the annual production of the synthetic macromolecular material of countries in the world surpasses 1.4 hundred million tons, about 4,000 ten thousand t/a of waste plastic, and increase just with surprising rapidity every year.Though macromolecular material will continue to play very effective Economic development platform action in Future Development, yet things always has positive and negative two aspects, offer convenience to people at macromolecular material, when making the life better quality, a large amount of plastic refuses after it uses are also growing with each passing day, particularly disposable polymer wrapping material, a part enters the municipal solid wastes treatment system in company with domestic refuse, and another part rests on exposed the stacking or the shallow embedding level with domestic refuse.Because most of synthesized polymer material erosion resistances are better, be difficult to decompose at occurring in nature, the physical environment of depending on for existence to people has caused very important negative impact.
For above-mentioned reasons, solve serious day by day " white pollution " problem and become people's question of common concern.The development work of degradative plastics now both at home and abroad is very active, and existing part begun suitability for industrialized production, develops quite rapid.Biodegradable plastic had both had the premium properties of performance plastics when using itself, and did not bring pollution to environment again when discarding with the back, can be by the rapid feature of decomposing of various biologies (enzyme).Therefore develop energetically and promote the environment biodegradable polymer, be only the method for taking stopgap measures and effecting a permanent cure, also meet the trend of current macromolecular material greenization.
One of main raw material of synthetic carbon dioxide-epoxy propane copolymer, carbonic acid gas is the CO that many industrial production field is produced
2Waste gas is discharged into and has not only caused environmental pollution in the atmospheric layer, and is the waste of carbon resource.Carbonic acid gas when being activated higher degree, with epoxide generation copolyreaction, generates carbon dioxide-epoxy propane copolymer under catalyst action, through aftertreatment, just obtain the carbonic acid gas resin material.Can be by the synthetic of carbon dioxide-epoxy propane copolymer with CO
2The resource immobilization, this has not only opened up new carbon resource, alleviates the shortage of petrochemical materials, and can protect human ecotope.On the other hand, the complete biodegradable characteristic of carbon dioxide-epoxy propane copolymer, the nonbiodegradable common plastics of the replacement of using can be widely used in wrapping material, table ware, daily use Sundry goods, disposable medical material, aspects such as operation stitching.For solving " white pollution " important meaning is arranged also
But carbon dioxide-epoxy propane copolymer is a class amorphism macromolecular material, and its second-order transition temperature has only about 34 ℃, therefore after temperature surpasses its second-order transition temperature, distortion can appear in the product that makes, and this has limited it to a great extent and has been extensive use of
Yet, by between molecular chain, introducing chemical bond, it is carried out crosslinked, can effectively overcome above-mentioned deficiency.In addition, the tridimensional network that crosslinked back forms can significantly improve its a lot of key properties, as wearability, chemical-resistant resistance, stress cracking resistance, and ageing resistance and viscous deformation's property etc.Shock strength and tensile strength are improved, and shrinkability descends, and low-temperature performance also improves.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of preparation method of crosslinked carbon dioxide-epoxy propane copolymer is provided.
Preparation method of the present invention is as follows:
The carbon dioxide-epoxy propane copolymer weight-average molecular weight of using is 5-20 ten thousand, and shared parts by weight are 100 parts;
The superoxide that uses is benzoyl peroxide (BPO), dicumyl peroxide (DCP), ditertiary butyl peroxide (DTBP), tert-butyl peroxide isopropyl benzene, 1,1-bis(t-butylperoxy)-3,3,5-trimethyl-cyclohexane, (2,5-dimethyl-2,5 di-t-butyl) the peroxy hexane, (2,5-dimethyl-2,5 di-t-butyls) peroxy hexin or 2, the 4-dichlorobenzoperoxide; Shared parts by weight are 0.05-1 part;
The silane coupling agent that uses is vinyltrimethoxy silane, and is a kind of in vinyltriethoxysilane and vinyl three ('beta '-methoxy oxyethyl group) silane; Shared parts by weight are 1-10 part;
The catalyzer that uses is dibutyl two (laurostearic acid) tin, stannous acetate or dibutyl two (sad) tin; Shared parts by weight are 0.01-0.3 part;
By proportioning carbon dioxide-epoxy propane copolymer, superoxide, silane coupling agent and catalyzer are mixed in Banbury mixer, temperature in the Banbury mixer is at 130-180 ℃, the blend time is 3-10 minute, with the resin after the blend 150 ℃ down hot-forming after, in 30-90 ℃ hot water crosslinked 4-96 hour, obtain a kind of crosslinked carbon dioxide-epoxy propane copolymer.Forming different measured gel contents according to sample is 15-85%, and the mechanical property scope is as follows: tensile strength is 30-45MPa, elongation at break 3-8%.
It is as follows that a kind of carbon dioxide-epoxy propane copolymer that cross-linking method of the present invention obtains, crosslinked back gel content can reach 85%. mechanical property scopes: tensile strength is 30-45MPa, elongation at break 3-8%.By the crosslinked effective range of application of expanding carbon dioxide-epoxy propane copolymer.
Embodiment
It is 100 parts of 50,000 carbon dioxide-epoxy propane copolymer parts by weight that embodiment 1. gets weight-average molecular weight, 0.05 part of benzoyl peroxide (BPO) parts by weight, 1 part of vinyltrimethoxy silane parts by weight, 0.01 part of dibutyl two (laurostearic acid) tin parts by weight.Above-mentioned substance is after height stirs machine and stirs, and 130 ℃ of following melt blendings are 3 minutes in Banbury mixer, with the resin after the blend 150 ℃ hot-forming down after, in 30 ℃ hot water crosslinked 4 hours, obtain a kind of crosslinked carbon dioxide-epoxy propane copolymer.Measured gel content is 15%, and mechanical property is as follows: tensile strength is 30MPa, elongation at break 3%.
It is 100 parts of 200,000 carbon dioxide-epoxy propane copolymer parts by weight that embodiment 2. gets weight-average molecular weight, 1 part of dicumyl peroxide (DCP) parts by weight, 10 parts of vinyltriethoxysilane parts by weight, 0.3 part of stannous acetate parts by weight.Above-mentioned substance is after height stirs machine and stirs, and 160 ℃ of following melt blendings are 10 minutes in Banbury mixer, with the resin after the blend 150 ℃ hot-forming down after, in 90 ℃ hot water crosslinked 96 hours, obtain a kind of crosslinked carbon dioxide-epoxy propane copolymer.Measured gel content is 85%, and mechanical property is as follows: tensile strength is 45MPa, elongation at break 8%.
It is 100 parts of 80,000 carbon dioxide-epoxy propane copolymer parts by weight that embodiment 3. gets weight-average molecular weight, 0.8 part of ditertiary butyl peroxide (DTBP) parts by weight, 5 parts of vinyl three ('beta '-methoxy oxyethyl group) silane parts by weight, 0.2 part of dibutyl two (sad) tin parts by weight, above-mentioned substance is after height stirs machine and stirs, 180 ℃ of following melt blendings are 8 minutes in Banbury mixer, with the resin after the blend 150 ℃ down hot-forming after, in 40 ℃ hot water crosslinked 72 hours, obtain a kind of crosslinked carbon dioxide-epoxy propane copolymer.Measured gel content is 60%, and mechanical property is as follows: tensile strength is 36Mpa, elongation at break 5%.
It is 100 parts of 160,000 carbon dioxide-epoxy propane copolymer parts by weight that embodiment 4. gets weight-average molecular weight, 0.7 part of tert-butyl peroxide isopropyl benzene parts by weight, 8 parts of vinyltriethoxysilane parts by weight, 0.2 part of dibutyl two (sad) tin parts by weight, above-mentioned substance is after height stirs machine and stirs, 170 ℃ of following melt blendings are 6 minutes in Banbury mixer, with the resin after the blend 150 ℃ down hot-forming after, in 50 ℃ hot water crosslinked 48 hours, obtain a kind of crosslinked carbon dioxide-epoxy propane copolymer.Measured gel content is 50%, and mechanical property is as follows: tensile strength is 35Mpa, elongation at break 7%.
It is 100 parts of 100,000 carbon dioxide-epoxy propane copolymer parts by weight that embodiment 5. gets weight-average molecular weight, 1,1-bis(t-butylperoxy)-3,3,0.7 part of 5-trimethyl-cyclohexane parts by weight, 8 parts of vinyltriethoxysilane parts by weight, 0.1 part of dibutyl two (sad) tin parts by weight, above-mentioned substance is after height stirs machine and stirs, 170 ℃ of following melt blendings are 6 minutes in Banbury mixer, with the resin after the blend 150 ℃ down hot-forming after, in 60 ℃ hot water crosslinked 72 hours, obtain a kind of crosslinked carbon dioxide-epoxy propane copolymer.Measured gel content is 33%, and mechanical property is as follows: tensile strength is 40Mpa, elongation at break 8%.
It is 100 parts of 150,000 carbon dioxide-epoxy propane copolymer parts by weight that embodiment 6. gets weight-average molecular weight, (2,5-dimethyl-2,5 di-t-butyls) peroxy hexane parts by weight are 0.7 part, 8 parts of vinyltriethoxysilane parts by weight, 0.1 part of dibutyl two (sad) tin parts by weight, above-mentioned substance is after height stirs machine and stirs, 170 ℃ of following melt blendings are 6 minutes in Banbury mixer, with the resin after the blend 150 ℃ down hot-forming after, in 70 ℃ hot water crosslinked 72 hours, obtain a kind of crosslinked carbon dioxide-epoxy propane copolymer.Measured gel content is 67%, and mechanical property is as follows: tensile strength is 36Mpa, elongation at break 6%.
It is 100 parts of 150,000 carbon dioxide-epoxy propane copolymer parts by weight that embodiment 7. gets weight-average molecular weight, (2,5-dimethyl-2,5 di-t-butyls) peroxy hexin parts by weight are 0.7 part, 5 parts of vinyltriethoxysilane parts by weight, 0.1 part of dibutyl two (sad) tin parts by weight, above-mentioned substance is after height stirs machine and stirs, 180 ℃ of following melt blendings are 6 minutes in Banbury mixer, with the resin after the blend 150 ℃ down hot-forming after, in 50 ℃ hot water crosslinked 48 hours, obtain a kind of crosslinked carbon dioxide-epoxy propane copolymer.Measured gel content is 32%, and mechanical property is as follows: tensile strength is 41Mpa, elongation at break 6%.
It is 100 parts of 150,000 carbon dioxide-epoxy propane copolymer parts by weight that embodiment 8. gets weight-average molecular weight, 2,0.7 part of 4-dichlorobenzoperoxide parts by weight, 5 parts of vinyltriethoxysilane parts by weight, 0.1 part of dibutyl two (sad) tin parts by weight, above-mentioned substance is after height stirs machine and stirs, 180 ℃ of following melt blendings are 6 minutes in Banbury mixer, with the resin after the blend 150 ℃ down hot-forming after, in 50 ℃ hot water crosslinked 48 hours, obtain a kind of crosslinked carbon dioxide-epoxy propane copolymer.Measured gel content is 19%, and mechanical property is as follows: tensile strength is 44Mpa, elongation at break 5%.
Claims (1)
1, a kind of preparation method of crosslinked carbon dioxide-epoxy propane copolymer, it is characterized in that step and condition are as follows: the carbon dioxide-epoxy propane copolymer weight-average molecular weight of using is 5-20 ten thousand; Shared parts by weight are 100 parts;
The superoxide that uses is benzoyl peroxide, dicumyl peroxide, ditertiary butyl peroxide, tert-butyl peroxide isopropyl benzene, 1,1-bis(t-butylperoxy)-3,3,5-trimethyl-cyclohexane, (2,5-dimethyl-2, the 5-di-t-butyl) the peroxy hexane, (2,5-dimethyl-2, the 5-di-t-butyl) peroxy hexin or 2, the 4-dichlorobenzoperoxide; Shared parts by weight are 0.05-1 part;
The silane coupling agent that uses is vinyltrimethoxy silane, and is a kind of in vinyltriethoxysilane and vinyl three ('beta '-methoxy oxyethyl group) silane; Shared parts by weight are 1-10 part;
The catalyzer that uses is dibutyl two (laurostearic acid) tin, stannous acetate or dibutyl two (sad) tin; Shared parts by weight are 0.01-0.3 part;
By proportioning carbon dioxide-epoxy propane copolymer, superoxide, silane coupling agent and catalyzer are mixed in Banbury mixer, temperature in the Banbury mixer is at 130-180 ℃, the blend time is 3-10 minute, with the resin after the blend 150 ℃ down hot-forming after, in 30-90 ℃ hot water crosslinked 4-96 hour, obtain a kind of crosslinked carbon dioxide-epoxy propane copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810050978A CN100586971C (en) | 2008-07-18 | 2008-07-18 | Method for preparing crosslinked carbon dioxide-propylene oxide copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810050978A CN100586971C (en) | 2008-07-18 | 2008-07-18 | Method for preparing crosslinked carbon dioxide-propylene oxide copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101319035A CN101319035A (en) | 2008-12-10 |
| CN100586971C true CN100586971C (en) | 2010-02-03 |
Family
ID=40179328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810050978A Expired - Fee Related CN100586971C (en) | 2008-07-18 | 2008-07-18 | Method for preparing crosslinked carbon dioxide-propylene oxide copolymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100586971C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106366252A (en) * | 2016-08-31 | 2017-02-01 | 李健 | Antistatic carbon dioxide resin material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1696197A (en) * | 2005-05-31 | 2005-11-16 | 中国科学院广州化学研究所 | Material of cross-linked poly methyl ethylene carbonate and preparation method |
| CN1775828A (en) * | 2005-11-21 | 2006-05-24 | 中国科学院长春应用化学研究所 | Method for preparing crosslinked aliphatic series polycarbonate |
| CN1793198A (en) * | 2005-11-21 | 2006-06-28 | 中国科学院长春应用化学研究所 | Process for improving friability and cold-flow of carbon dioxide epoxy propylane copolymer |
-
2008
- 2008-07-18 CN CN200810050978A patent/CN100586971C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1696197A (en) * | 2005-05-31 | 2005-11-16 | 中国科学院广州化学研究所 | Material of cross-linked poly methyl ethylene carbonate and preparation method |
| CN1775828A (en) * | 2005-11-21 | 2006-05-24 | 中国科学院长春应用化学研究所 | Method for preparing crosslinked aliphatic series polycarbonate |
| CN1793198A (en) * | 2005-11-21 | 2006-06-28 | 中国科学院长春应用化学研究所 | Process for improving friability and cold-flow of carbon dioxide epoxy propylane copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101319035A (en) | 2008-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107629426B (en) | Bamboo fiber/polylactic acid composite material and preparation method thereof | |
| CN102827465B (en) | Degradable biobased thermoplastic vulcanized rubber | |
| CN101250306B (en) | High-toughness thermoplastic elastomer/polystyrene composite material and preparation method thereof | |
| Wang et al. | Sustainable developments in polyolefin chemistry: Progress, challenges, and outlook | |
| Thitithammawong et al. | Effect of different types of peroxides on rheological, mechanical, and morphological properties of thermoplastic vulcanizates based on natural rubber/polypropylene blends | |
| CN103642184B (en) | Dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastomer and preparation method thereof | |
| CN107474374B (en) | A kind of lignin/polyolefin thermoplastic elastomer composite material and preparation method | |
| CN112080115B (en) | High-toughness polylactic acid composite material for environment-friendly tableware and preparation method thereof | |
| CN101157793B (en) | Heat-proof polylactic acid blend and preparation method thereof | |
| CN107383475A (en) | A kind of lignin/nitile-butadiene rubber composite material and preparation method thereof | |
| CN101319032B (en) | Method for preparing crosslinked polylactic acid | |
| CN110172240A (en) | Damping encapsulated ABS thermoplastic elastomer (TPE) and its manufacturing method | |
| CN108285575B (en) | Cup cover | |
| CN104710693B (en) | Low-temperature-resistant door/window sealing strip and preparation method thereof | |
| CN100586971C (en) | Method for preparing crosslinked carbon dioxide-propylene oxide copolymer | |
| CN101319034A (en) | Method for preparing crosslinked poly-succinic butanediol ester | |
| KR101124989B1 (en) | Polylactic acid Composites | |
| CN111875872B (en) | EVA/PEBAX supercritical foaming composite shoe material and preparation method thereof | |
| CN1544525A (en) | Method for preparing biodegradable poly-lactic acid foam plastic | |
| Ghani et al. | Properties of tyre dust-filled low density polyethylene composites: the effect of phthalic anhydride | |
| KR20110089724A (en) | Polypropylene-polylactic acid composites | |
| CN107400344A (en) | Ultra-toughness PLA/NBR bio-based thermoplastic sulfurized rubbers with shape memory function and preparation method thereof | |
| CN100484999C (en) | Super malleable nylon and its preparing method | |
| WO2018129779A1 (en) | Polyolefin thermoplastic elastomer and processing method therefor | |
| CN1890267A (en) | Rubbery product or rubbery substance containing product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100203 Termination date: 20160718 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |