CN107325280A - A kind of polyetheramide elastomeric body material of high fondant-strength and preparation method thereof - Google Patents
A kind of polyetheramide elastomeric body material of high fondant-strength and preparation method thereof Download PDFInfo
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- CN107325280A CN107325280A CN201710674959.7A CN201710674959A CN107325280A CN 107325280 A CN107325280 A CN 107325280A CN 201710674959 A CN201710674959 A CN 201710674959A CN 107325280 A CN107325280 A CN 107325280A
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- elastomeric body
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
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Abstract
The present invention relates to a kind of polyetheramide elastomeric body material of high fondant-strength, polyetheramide elastomeric body material is formed by long carbon chain nylon, polyethers and branching agent copolymerization, wherein being by mass percentage：Polyethers 85 15%；Long carbon chain nylon 15 85%, the content of branching agent accounts for the 0.05 ~ 5% of polyethers and long carbon chain nylon gross mass, and long carbon chain nylon is AABB types polyamide or AB type polyamide.One-step synthesis method is used during preparation.Preparation method of the present invention is simple, and step is easily operated, the polyetheramide elastomeric body material molten good moldability prepared, and with preferable flexibility and elasticity, viscosity and melt strength are greatly increased, and can be more broadly useful for foaming field.
Description
Technical field
The present invention relates to polyetheramide elastomeric body material of a kind of high fondant-strength and preparation method thereof, belong to polymer system
Standby technical field.
Background technology
Polyetheramides analog thermoplastic elastomer is a kind of block copolymer, be by dystectic crystallinity polyamide hard section and
Amorphism or amorphous polyester or polyester soft segment composition.Their chemical composition, fragment length and between ratio determine
The physics and chemical property of such material.Polyamide elastomer intensity is high, high, the elastic good, proportion of toughness is low, resist bending is tired
Performance is good, anti-wear performance is good, low temperature performance well, can be widely applied to automobile, sporting goods, medical supplies, seal, machine
In terms of tool parts.But viscosity is relatively low after the melting of polyetheramide elastomeric body, melt strength is poor, and foaming is difficult so that
Its application in foam of polymers field is very restricted, it is necessary to made improvements.
The content of the invention
The invention aims to solve the above problems, there is provided a kind of polyetheramide elastomeric body material of high fondant-strength
Material and preparation method thereof, preparation method is simple, and step is easily operated, and the polyetheramide elastomeric body material prepared can be used in
Foam art.
The present invention is adopted the following technical scheme that：A kind of polyetheramide elastomeric body material of high fondant-strength, the polyethers acyl
Amine elastomeric material is formed by long carbon chain nylon, polyethers and branching agent copolymerization, wherein being by mass percentage：Polyethers 85-
15%；Long carbon chain nylon 15-85%, the content of branching agent accounts for the 0.05~5% of polyethers and long carbon chain nylon gross mass, the length
Carbon chain nylon is AABB types polyamide or AB type polyamide.
Further, the AABB types polyamide is polymerized by dicarboxylic acids and diamines, and the dicarboxylic acids is carbon number 6
~20 α, ω-straight-chain aliphatic dicarboxylic acids, the diamines are the α of carbon number 6~20, ω-straight-chain aliphatic diamines.
Further, the molecular weight of the polyethers is 200~3000g/mol hydroxy-end capped polyethers or amino-terminated
Polyethers.
Further, the branching agent is polyalcohol or polyacid.
Further, the relative viscosity of the polyetheramide elastomeric body is 3.0~3.6, and melt strength is 28-32cN.
The preparation method of the polyetheramide elastomeric body material of high fondant-strength, using one-step synthesis method, comprises the following steps：
Raw material is positioned in reactor in proportion, by mass percentage for：Polyethers 85-15%；Long carbon chain nylon 15-
85%, the content of branching agent accounts for the 0.05~5% of polyethers and long carbon chain nylon gross mass, and adds urging for phosphorous atomic compound
Agent；Add and temperature is heated to after being stirred after aqueous solvent for 175-185 DEG C, pressure is 0.8-1.0Mpa, the row of opening
Air valve, discharge vapor maintenance reaction kettle pressure is 0.8-1.0Mpa, is reacted after 1.5-2.5h, opens air bleeding valve and is slowly depressured,
Temperature is raised simultaneously to 220-250 DEG C, after pressure reaches normal pressure in kettle, is closed air bleeding valve, is vacuumized, make the vacuum in kettle be
1.5-2.5h is reacted at 180-200Pa, 220-250 DEG C of temperature, polyetheramide elastomeric body material is obtained.
Further, the addition of the catalyst is the 0.05%~0.1% of polyethers and long carbon chain nylon gross mass.
The catalyst of the phosphorous atomic compound is phosphoric acid, hypophosphorous acid, phosphorous acid, dimethylphosphinic acid, phenyl methyl
Phosphinic acids, hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, hypophosphorous acid lithium, hypophosphorous acid ethyl ester, phenyl-phosphonite, phenyl-phosphonite sodium,
Phenyl-phosphonite potassium, phenyl-phosphonite lithium, phenyl-phosphonite ethyl ester, phenyl-phosphonic acid, ethylphosphonic acid, phenyl-phosphonic acid sodium, Phenylphosphine
Sour potassium, phenyl-phosphonic acid lithium, phenyl-phosphonic acid diethylester, ethylphosphonic acid sodium, ethyl phosphonic acid potassium, sub- phosphorous acid, hydrogen phosphite sodium, phosphorous
Sour sodium, triethyl phosphite, triphenyl phosphite or pyrophosphorous acid
Preparation method of the present invention is simple, and step is easily operated, the polyetheramide elastomeric body material molten shaping prepared
Property is good, and with preferable flexibility and elasticity, viscosity and melt strength are greatly increased, and can be more broadly useful for being foamed into V-neck V
Domain.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated.
Embodiment 1：
A kind of preparation method of the polyetheramide elastomeric body material of high fondant-strength, using one-step synthesis method, including it is as follows
Step：
By decanedioyl decamethylene diamine salt 2kg, polyether diamine (ED-900) 2kg, deionized water 5kg, the last of the ten Heavenly stems
Diacid 0.5kg, citric acid 5g, phosphatase 24 g add reactor, and stirring is heated to 180 DEG C, pressure 1.0Mpa opens exhaust
Valve, discharge vapor maintenance reaction kettle pressure 1.0Mpa.After reaction 2 hours, air bleeding valve slowly release is opened, while making reaction warm
Degree is raised to 250 DEG C.After pressure is normal pressure in kettle, drain tap is closed, reactor is vacuumized.Maintain vacuum 500Pa, temperature
2h is reacted at 250 DEG C, polyetheramide elastomeric body is obtained
Embodiment 2：
A kind of preparation method of the polyetheramide elastomeric body material of high fondant-strength, using one-step synthesis method, including it is as follows
Step：
By decanedioic acid 2.7kg, decamethylene diamine 1.72kg, 5kg deionized water, PTMG1000 1.5kg, glycerine 8g, phosphorous acid
5g adds reactor, adds reactor, and stirring is heated to 180 DEG C, pressure 1.0Mpa opens air bleeding valve, discharges vapor
Maintenance reaction kettle pressure 1.0Mpa.After reaction 2 hours, air bleeding valve slowly release is opened, while allowing reaction temperature to be raised to 250 DEG C.
After pressure is normal pressure in kettle, drain tap is closed, reactor is vacuumized.Maintain to react 2h at vacuum 500Pa, 250 DEG C of temperature,
Obtain polyetheramide elastomeric body.
Embodiment 3：
The preparation method of the polyetheramide elastomeric body material of high fondant-strength, using one-step synthesis method, comprises the following steps：
By decanedioyl decamethylene diamine salt 2kg, polyether diamine (ED-900) 2kg, deionized water 5kg, the last of the ten Heavenly stems
Diacid 0.5kg, citric acid 5g, phosphoric acid 2g add reactor, stir, and are heated to 180 DEG C, pressure 1.0Mpa is opened
Air bleeding valve, discharges after vapor maintenance reaction kettle pressure 1.0Mpa, reaction 2h, air bleeding valve slowly release is opened, while allowing reaction
Temperature is raised to 250 DEG C.After pressure is normal pressure in kettle, drain tap is closed, reactor is vacuumized.Maintain vacuum 500Pa, temperature
2h is reacted at 250 DEG C, polyetheramide elastomeric body is obtained.
Embodiment 4：
The preparation method of the polyetheramide elastomeric body material of high fondant-strength, using one-step synthesis method, comprises the following steps：
By 12-aminolauric acid (AB types polyamide) 2kg, polyether diamine (D-400) (polyethers)
3kg, deionized water 5kg, decanedioic acid 0.5kg, citric acid 6g, phosphorous acid 2g add reactor, and stirring is heated to 180 DEG C,
Pressure 1.0Mpa, opens air bleeding valve, discharge vapor maintenance reaction kettle pressure 1.0Mpa.After reaction 2 hours, air bleeding valve is opened slow
Slow release, while allowing reaction temperature to be raised to 250 DEG C.After pressure is normal pressure in kettle, drain tap is closed, reactor is vacuumized.
Maintain to react 2 hours at vacuum 200Pa, 250 DEG C of temperature, obtain polyetheramide elastomeric body.
Embodiment 5：
The preparation method of the polyetheramide elastomeric body material of high fondant-strength, using one-step synthesis method, comprises the following steps：
Raw material is positioned in reactor in proportion, by mass percentage for：Polyethers 85%；Long carbon chain nylon 15%,
The content of branching agent accounts for the 0.05% of polyethers and long carbon chain nylon gross mass, and adds the catalyst of phosphorous atomic compound, will
Raw material adds reactor, and stirring is heated to 175 DEG C, pressure 1.0Mpa opens air bleeding valve, discharges vapor maintenance reaction
Kettle pressure 1.0Mpa.React after 2.5h, air bleeding valve slowly release is opened, while allowing reaction temperature to be raised to 220 DEG C.When pressure in kettle
After normal pressure, drain tap is closed, reactor is vacuumized.Maintain to react 1.5h at vacuum 180Pa, 220 DEG C of temperature, obtain polyethers
Amide elastomer.
Embodiment 6：
The preparation method of the polyetheramide elastomeric body material of high fondant-strength, using one-step synthesis method, comprises the following steps：
Raw material is positioned in reactor in proportion, by mass percentage for：Polyethers 15%；Long carbon chain nylon 85%,
The content of branching agent accounts for the 5% of polyethers and long carbon chain nylon gross mass, and adds the catalyst of phosphorous atomic compound, by raw material
Reactor is all added, stirring is heated to 185 DEG C, pressure 0.8Mpa opens air bleeding valve, discharges vapor maintenance reaction
Kettle pressure 1.0Mpa.React after 2.5h, air bleeding valve slowly release is opened, while allowing reaction temperature to be raised to 250 DEG C.When pressure in kettle
After normal pressure, drain tap is closed, reactor is vacuumized.Maintain to react 2.5h at vacuum 200Pa, 250 DEG C of temperature, obtain polyethers
Amide elastomer.
The polyetheramide elastomeric body material prepared in Example 1-4 carries out the inspection of relative viscosity and melt strength
Survey, as a result as shown in table 1.
(1) measure of relative viscosity
Accurate weighing 0.2g samples, stirring and dissolving is in the sulfuric acid of 25ml 96% at 20~30 DEG C., will be molten after being completely dissolved
Liquid is put into dark type viscometer, and lowering time (t) is determined at 25 DEG C.Same method determines the lowering time of 96% sulfuric acid
(t0).Relative viscosity can be obtained by following formula：
Relative viscosity=t/t0
(2) measure of melt strength
Melted using the Geottfert Rheotens of German Geottfert Werkstoff Pruefmaschinen companies
Body intensity meter determines melt strength.It is fed using Brabender extruders, screw diameter is 19mm, charging rate 8g/min.Machine
Head plus a capillary, long 30mm, diameter 2mm.200~230 DEG C of melt temperature during test, polyetheramide elastomeric body melt goes out die orifice
Clamped and drawn with two rotating wheels afterwards, traction acceleration is 20mm/s2 until fracture.Determine corresponding power during fracture
Value, that is, stretch force value, the force value reflects the melt strength of polyetheramide elastomeric body under the test condition.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Relative viscosity | 3.0 | 3.2 | 3.4 | 3.1 |
| Melt strength (cN) | 28 | 32 | 33 | 30 |
As shown in Table 1, the polyetheramide elastomeric body material obtained using the preparation method of the present invention has preferable melt
Intensity, can be used in foam art.
Claims (7)
1. a kind of polyetheramide elastomeric body material of high fondant-strength, it is characterised in that：The polyetheramide elastomeric body material by
Long carbon chain nylon, polyethers and branching agent copolymerization are formed, wherein being by mass percentage：Polyethers 85-15%；Long carbon chain nylon 15-
85%, the content of branching agent accounts for polyethers and 0.05 ~ 5 % of long carbon chain nylon gross mass, and the long carbon chain nylon is poly- for AABB types
Acid amides or AB type polyamide.
2. the polyetheramide elastomeric body material of high fondant-strength as claimed in claim 1, it is characterised in that：The AABB types gather
Acid amides is polymerized by dicarboxylic acids and diamines, and the dicarboxylic acids is the α of carbon number 6 ~ 20, ω-straight-chain aliphatic dicarboxylic acids,
The diamines is the α of carbon number 6 ~ 20, ω-straight-chain aliphatic diamines.
3. the polyetheramide elastomeric body material of high fondant-strength as claimed in claim 1, it is characterised in that：Point of the polyethers
Hydroxy-end capped polyethers or amino-terminated polyethers that son amount is 200 ~ 3000 g/mol.
4. the polyetheramide elastomeric body material of high fondant-strength as claimed in claim 1, it is characterised in that：The branching agent is
Polyalcohol or polyacid.
5. the polyetheramide elastomeric body material of high fondant-strength as claimed in claim 1, it is characterised in that：The polyetheramides
The relative viscosity of elastomer is 3.0 ~ 3.6, and melt strength is 28-32cN.
6. the preparation method of the polyetheramide elastomeric body material of the high fondant-strength described in claim 1, it is characterised in that：Using
One-step synthesis method, comprises the following steps：
Raw material is positioned in reactor in proportion, by mass percentage for：Polyethers 85-15%；Long carbon chain nylon 15-85%,
The content of branching agent accounts for polyethers and 0.05 ~ 5 % of long carbon chain nylon gross mass, and adds the catalysis of phosphorous atomic compound
Agent；Add and temperature is heated to after being stirred after aqueous solvent for 175-185 DEG C, pressure is 0.8-1.0Mpa, open exhaust
Valve, discharge vapor maintenance reaction kettle pressure is 0.8-1.0Mpa, is reacted after 1.5-2.5h, opens air bleeding valve and is slowly depressured, together
Shi Shenggao temperature is to 220-250 DEG C, after pressure reaches normal pressure in kettle, closes air bleeding valve, vacuumizes, makes the vacuum in kettle be
1.5-2.5h is reacted at 180-200 Pa, 220-250 DEG C of temperature, polyetheramide elastomeric body material is obtained.
7. the preparation method of the polyetheramide elastomeric body material of high fondant-strength as claimed in claim 6, it is characterised in that：Institute
The addition for stating catalyst is the 0.05% ~ 0.1% of polyethers and long carbon chain nylon gross mass.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710674959.7A CN107325280A (en) | 2017-08-09 | 2017-08-09 | A kind of polyetheramide elastomeric body material of high fondant-strength and preparation method thereof |
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| CN201710674959.7A CN107325280A (en) | 2017-08-09 | 2017-08-09 | A kind of polyetheramide elastomeric body material of high fondant-strength and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3093725A1 (en) | 2019-03-15 | 2020-09-18 | Arkema France | Rigid block and branched soft block copolymers |
| FR3114097A1 (en) * | 2020-09-15 | 2022-03-18 | Arkema France | Foamable composition of polymers comprising a copolymer with polyamide blocks and with branched polyether blocks |
| CN114213665A (en) * | 2021-12-28 | 2022-03-22 | 无锡殷达尼龙有限公司 | Preparation method of polyamide elastomer |
| CN114940755A (en) * | 2022-07-04 | 2022-08-26 | 华润化学材料科技股份有限公司 | Polyamide elastomer and preparation method thereof |
| CN115093700A (en) * | 2022-07-04 | 2022-09-23 | 华润化学材料科技股份有限公司 | Nylon elastomer material and preparation method thereof |
| CN115746557A (en) * | 2022-12-21 | 2023-03-07 | 无锡殷达尼龙有限公司 | Toughened long carbon chain nylon and preparation method and application thereof |
| CN116096794A (en) * | 2020-09-15 | 2023-05-09 | 阿科玛法国公司 | Polymer foam comprising ethylene-vinyl acetate (EVA) copolymer and/or ethylene-alkyl (meth) acrylate copolymer and copolymer comprising polyamide blocks and polyether blocks |
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| CN105566639A (en) * | 2016-02-01 | 2016-05-11 | 中国科学院化学研究所 | Polyamide 1012 serial thermoplastic elastomer material and preparation method thereof |
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| US6300463B1 (en) * | 1999-01-29 | 2001-10-09 | E. I. Du Pont De Nemours And Company | Thermoplastic elastomers |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3093725A1 (en) | 2019-03-15 | 2020-09-18 | Arkema France | Rigid block and branched soft block copolymers |
| WO2020188210A1 (en) | 2019-03-15 | 2020-09-24 | Arkema France | Branched hard- and soft-block copolymers |
| CN113574095A (en) * | 2019-03-15 | 2021-10-29 | 阿科玛法国公司 | Branched hard and soft block copolymers |
| CN113574095B (en) * | 2019-03-15 | 2023-10-24 | 阿科玛法国公司 | Branched hard block and soft block copolymers |
| CN116096794A (en) * | 2020-09-15 | 2023-05-09 | 阿科玛法国公司 | Polymer foam comprising ethylene-vinyl acetate (EVA) copolymer and/or ethylene-alkyl (meth) acrylate copolymer and copolymer comprising polyamide blocks and polyether blocks |
| WO2022058679A1 (en) * | 2020-09-15 | 2022-03-24 | Arkema France | Foamable polymer composition comprising a branched copolymer containing polyamide blocks and polyether blocks |
| CN116113658A (en) * | 2020-09-15 | 2023-05-12 | 阿科玛法国公司 | Foamable polymer composition comprising branched copolymer comprising polyamide blocks and polyether blocks |
| FR3114097A1 (en) * | 2020-09-15 | 2022-03-18 | Arkema France | Foamable composition of polymers comprising a copolymer with polyamide blocks and with branched polyether blocks |
| CN114213665A (en) * | 2021-12-28 | 2022-03-22 | 无锡殷达尼龙有限公司 | Preparation method of polyamide elastomer |
| CN114940755A (en) * | 2022-07-04 | 2022-08-26 | 华润化学材料科技股份有限公司 | Polyamide elastomer and preparation method thereof |
| CN115093700A (en) * | 2022-07-04 | 2022-09-23 | 华润化学材料科技股份有限公司 | Nylon elastomer material and preparation method thereof |
| CN114940755B (en) * | 2022-07-04 | 2024-03-01 | 华润化学材料科技股份有限公司 | Polyamide elastomer and preparation method thereof |
| CN115746557A (en) * | 2022-12-21 | 2023-03-07 | 无锡殷达尼龙有限公司 | Toughened long carbon chain nylon and preparation method and application thereof |
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Application publication date: 20171107 |