CN105367785A - Transparent nylon and preparation method therefor - Google Patents
Transparent nylon and preparation method therefor Download PDFInfo
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- CN105367785A CN105367785A CN201510837538.2A CN201510837538A CN105367785A CN 105367785 A CN105367785 A CN 105367785A CN 201510837538 A CN201510837538 A CN 201510837538A CN 105367785 A CN105367785 A CN 105367785A
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Abstract
The present invention discloses transparent nylon and a preparation method therefor. The transparent nylon comprises branched alkyl diamine units and oxalic acid units. The preparation method comprises: under inert gas and at a temperature of 30 DEG C-120 DEG C, slowly adding a diamine into an oxalic diester or adding the oxalic diester to the diamine, and carrying out a reaction for 2-6 hours to obtain a prepolymer, wherein the diamine is a branched alkyl diamine or a mixture of branched alkyl amines; and performing melt polymerization for 2-5 hours on the prepolymer to obtain a transparent nylon product at an ordinary pressure or a reduced pressure. The present invention provides a brand new aliphatic transparent nylon and a preparation method therefor. The nylon not only has an excellent transparency performance, but also has good characteristics of low water absorption, good dimensional stability, high flexibility, easy processing and high strength, and has a huge application prospect.
Description
Technical field
The present invention relates to a kind of transparent nylon and preparation method thereof.Synthesized transparent nylon has that water-intake rate is low, excellent in dimensional stability, good toughness, be easy to the good characteristics such as processing, intensity is high, has very high application prospect.
Background technology
Develop in the world after the first synthon-nylon from American scientist Tomas Carothers (Carothers), the comprehensive good characteristic of Yin Nilong, makes it be widely used in social production.Along with the quickening of the large production process of socialization, more Gao Geng great is incited somebody to action to the demand of nylon.
But at some special occasions, the such as transparency of nylon is poor, and the shortcomings such as water-intake rate is high significantly limit its Application Areas.Transparent nylon has the advantages such as the transparency is good compared with general nylon, not only can be used for drink and food packaging, also can be used as the wrapping material of precision instrument, instrument, medication chemistry, the cushion of production protection against the tide, shock absorbing and foaming plate etc., have the performances such as good tensile strength, impact strength, rigidity, wear resistance, chemical resistant properties, surface hardness.
Existing transparent nylon mainly contains two classes: aromatic series transparent nylon and semi-aromatic transparent nylon.But aromatic series transparent nylon, semi-aromatic transparent nylon is because of the existence of aromatic monomer, and polymerization temperature is high, easy to change, and building-up process is more complicated, and complete processing also requires harshness.
Summary of the invention
To be solved by this invention is that existing transparent nylon polymerization temperature is high, easy to change, and building-up process is complicated and complete processing requires harsh technical problem.
In order to solve the problem, the invention provides a kind of transparent nylon, it is characterized in that, it contains branched-chain alkyl diamine unit and oxalic acid unit.
Preferably, described branched-chain alkyl diamine unit is trimethylhexamethylenediamine unit.
Preferably, it is also the straight-chain aliphatic diamine unit of 4 ~ 12 containing carbonatoms, and the molar content of straight-chain aliphatic diamine unit in all diamine unit is 1 ~ 50mol%.
Preferably, described oxalic acid unit comes from oxalate diester, be selected from dimethyl oxalate, oxalic acid diethyl ester, DPO, oxalic acid diisopropyl ester, dibutyl oxalate, di-isobutyl oxalate or oxalic acid di tert butyl carbonate any one or multiple.
Preferably, with 95% sulfuric acid for solvent, working concentration is the relative viscosity that the transparent nylon solution of 0.01g/mL measures at 25 DEG C is 1.2 ~ 6.0.
Present invention also offers the preparation method of above-mentioned transparent nylon, it is characterized in that, comprise the following steps:
Step 1): at the temperature of inert gas and 30 DEG C-120 DEG C, diamine is slowly added in and joins in diamine in oxalate diester or by oxalate diester, react and obtain prepolymer after 2-6 hour; Wherein diamine is branched-chain alkyl diamines or branched-chain alkyl diamine mixture;
Step 2): under normal or reduced pressure, prepolymer melt polymerization is obtained transparent nylon product in 2-5 hour.
Preferably, described branched-chain alkyl diamine unit is trimethylhexamethylenediamine unit.
Preferably, the mixture of described branched-chain alkyl diamine mixture to be trimethylhexamethylenediamine and carbonatoms the be straight-chain aliphatic diamines arbitrary proportion of 4 ~ 12.
Transparent nylon provided by the invention contains side chain diamine unit and oxalic acid unit.For side chain diamine unit, the present invention is not particularly limited, but considers the crystal property that will destroy nylon product, and ensure the transparency of nylon, side chain diamines with asymmetry diamines as well; Same reason side chain with more than 2 and two as well, there to be unsymmetrical carbon as well.Be preferably trimethylhexamethylenediamine.For trimethylhexamethylenediamine, it both can be 2,2,4-trimethylhexamethylenediamine, also can be 2,4,4-trimethylhexamethylenediamine, can also be the mixture of the two.
Straight-chain aliphatic diamine unit can also be introduced in transparent nylon of the present invention.The kind of the present invention to straight-chain aliphatic diamine unit is also not particularly limited.Generally with carbonatoms be the straight-chain aliphatic diamine unit of 4 ~ 18 as well; When this unit composition be selected from carbonatoms lower than 4 time, product viscosity will be caused too low; When this unit composition be selected from carbonatoms higher than 18 time, diamines raw materials cost will be improved.Preferred carbonatoms is the straight-chain aliphatic diamine unit of 4 ~ 12, and more preferably carbonatoms is the straight-chain aliphatic diamine unit of 6 ~ 12.
In the present invention, the content of straight-chain aliphatic diamine unit in all diamine unit is not particularly limited, but considers the transparency that will ensure product, destroy the crystal property of nylon product, and the content of straight-chain aliphatic diamine unit is unsuitable too high.Generally with 1 ~ 80mol% as well, be preferably 1 ~ 60mol%, more preferably 1 ~ 60mol%, most preferably be 1 ~ 50mol%.
The present invention is to described trimethylhexamethylenediamine (2,2,4-and 2, the mixture of 4,4-position) beyond unit carbonatoms be 4 ~ 18 straight-chain aliphatic diamine unit be not particularly limited, but consider the ease of polymerization and raw materials cost, general preferably Putriscine, 1,5-pentamethylene diamine, 1,6-hexanediamine, 1,7-heptamethylene diamine, 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 1, one or more in 11-undecane diamines, 1,12-dodecamethylene diamine.
The present invention is not particularly limited described oxalic acid unit source, but consider the ease of polymerization, general selection oxalate diester, be preferably in dimethyl oxalate, oxalic acid diethyl ester, DPO, oxalic acid diisopropyl ester, dibutyl oxalate, di-isobutyl oxalate or oxalic acid di tert butyl carbonate one or more.
The molecular weight of a kind of transparent nylon obtained by the present invention is not particularly limited, with 95% sulfuric acid for solvent, working concentration be the relative viscosity that measures at 25 DEG C of the transparent nylon solution of 0.01g/mL in 1.2 ~ 6.0 scopes, more preferably 2.0 ~ 4.8.Be particularly preferably 2.5 ~ 3.5.When relative viscosity lower than 2.0 time, molecular weight of product may be lower, and mechanical property is poor.When relative viscosity higher than 6.0 time, melt viscosity may uprise, and affects processability.
In preparation process, also can add solvent in reaction system if desired.The present invention was not particularly limited the reaction times described in when preparing prepolymer.But consider that the reaction times is long, affect reaction cost.Reaction times is too short, and polymer conversion is lower, causes mechanical properties of polymer to reduce.Therefore generally with 2-6 hour as well, be preferably 3-6 hour, be particularly preferably 4-5 hour.
The present invention is not particularly limited the temperature of reaction described in when preparing prepolymer.But consider that temperature of reaction is too high, cause polymer unwinds.Temperature of reaction is too low, and polymericular weight is lower, and viscosity is lower.Therefore generally with 30 DEG C-120 DEG C hours as well, be preferably 50 DEG C-120 DEG C, be particularly preferably 80 DEG C-120 DEG C.
The present invention was not particularly limited the reaction times described in during melt polymerization.But consider that the reaction times is long, side reaction occurs, affects polymkeric substance quality and color and luster.Reaction times is too short, and polymericular weight is lower, and viscosity is lower.Therefore generally with 2-5 hour as well, be preferably 2-4 hour, be particularly preferably 2.5-4 hour.
The present invention is not particularly limited described a kind of diamine mixture prepared in the method for transparent nylon, is the mixture of the straight-chain aliphatic diamines of 4 ~ 18 for trimethylhexamethylenediamine and carbonatoms; At least containing the one in 2,2,4-trimethylhexamethylenediamine and 2,4,4-trimethylhexamethylenediamine in mixture.
Compared with prior art, beneficial effect of the present invention is:
The invention provides a kind of brand-new aliphatics transparent nylon and preparation method thereof.This nylon not only has excellent properties of transparency, and water-intake rate is low, excellent in dimensional stability, good toughness, be easy to the good characteristics such as processing, intensity is high, has very high application prospect.
Accompanying drawing explanation
Fig. 1 is the DSC curve of a kind of transparent nylon prepared by embodiment 1.
Embodiment
For making the present invention become apparent, hereby with preferred embodiment, and accompanying drawing is coordinated to be described in detail below.
Embodiment
In embodiment 1-7:
One, parameter interpretation
(1) relative sulfuric acid viscosity:
The relative viscosity that concentration is 0.01g/mL transparent nylon is measured in 96% vitriol oil of 25 DEG C.
(2) thermal property:
Adopt TADSC-Q100 analytical instrument, get about 5mg sample, test condition is as follows: in a nitrogen atmosphere, and gained transparent nylon is warmed up to 300 DEG C from 30 DEG C; 30 DEG C are dropped to the rate of temperature fall of 20 DEG C/min after 2 minutes at 300 DEG C of constant temperature; At 30 DEG C, constant temperature is after 2 minutes, is again warmed up to 300 DEG C with the heat-up rate of 20 DEG C/min.Second-order transition temperature is determined from DSC second time heating curve.
(3) 23 DEG C of saturated water absorptions:
After polymeric amide being hot pressed into thickness 0.5mm film, water polyamide layer being put into 23 DEG C weighs (W1) to constant weight; Then sample is dried to constant weight (W2) in the vacuum drying oven of 100 DEG C, saturated water absorption is:
Saturated water absorption=(W1-W2)/W2*100%.
Two, explanation is called for short:
TMD: trimethylhexamethylenediamine (mixture of 2,2,4-and 2,4,4-position); DA12:1,12-dodecyl diamines; DA6:1,6-hexanediamine; DA4:1,4-butanediamine; DBuO: dibutyl oxalate; DEO: oxalic acid diethyl ester; DBO: phenyloxalate; .
Wherein, TMD: purity is 98%, purchased from TCI company.
DA4: purity is 98%, purchased from Sigma-Aldrich company.
DA6: purity is 98%, purchased from Sigma-Aldrich company.
DA12: purity is 98%, purchased from Sigma-Aldrich company.
DBuO: purity is 99%, purchased from Sigma-Aldrich company.
DEO: purity is 99%, purchased from Sigma-Aldrich company.
DBO: purity is 99%, purchased from Sigma-Aldrich company.
Embodiment 1
By trimethylhexamethylenediamine (2,2,4-and 2,4, the mixture of 4-position) 158.28g and 1000mL toluene joins in 2L four-hole boiling flask, replace nitrogen 3 times under mechanical stirring and system is warmed up to 60 DEG C, in 1 hour, dripping dibutyl oxalate 202.25g by normal pressure funnel subsequently.Dropwise rear continuation backflow three hours.Toluene distillation is complete, nitrogen replacement three times, and 2-3torr was decompressed in 20 minutes, also melt polymerization 2h, cooling obtain transparent products to be at this temperature warming up to 200 DEG C.After measured, its relative viscosity is 2.5, and glass transition temperature Tg is 65 DEG C, and saturated water absorption is 1.1%.
The DSC curve of the product that embodiment 1 is obtained as shown in Figure 1.
Embodiment 2
By trimethylhexamethylenediamine (2,2,4-and 2,4, the mixture of 4-position) 158.28g and 1000mL toluene joins in 2L four-hole boiling flask, replace nitrogen 3 times under mechanical stirring and system is warmed up to 60 DEG C, in 1 hour, dripping oxalic acid diethyl ester 146.14g by normal pressure funnel subsequently.Dropwise rear continuation backflow three hours.Toluene distillation is complete, nitrogen replacement three times, and 2-3torr was decompressed in 20 minutes, also melt polymerization 3h, cooling obtain transparent products to be at this temperature warming up to 200 DEG C.After measured, its relative viscosity is 2.2, and glass transition temperature Tg is 65 DEG C, and saturated water absorption is 1.1%.
Embodiment 3
By trimethylhexamethylenediamine (2,2,4-and 2,4, the mixture of 4-position) 158.28g and 800mL toluene joins in 2L four-hole boiling flask, replace nitrogen 3 times under mechanical stirring and system is warmed up to 60 DEG C. dimethyl oxalate 118.09 is dissolved in 200mL toluene, was added drop-wise in four-hole boiling flask in 1 hour by normal pressure funnel subsequently.Dropwise rear continuation backflow three hours.Toluene distillation is complete, nitrogen replacement three times, and 2-3torr was decompressed in 20 minutes, also melt polymerization 4h, cooling obtain transparent products to be at this temperature warming up to 200 DEG C.After measured, its relative viscosity is 1.9, and glass transition temperature Tg is 65 DEG C, and saturated water absorption is 1.1%.
Embodiment 4
By trimethylhexamethylenediamine (2,2,4-and 2,4, the mixture of 4-position) 79.14g, 1,12 diamino dodecane 100.18g and 500mL toluene join in 2L four-hole boiling flask, replace nitrogen 3 times under mechanical stirring and system is warmed up to 60 DEG C. phenyloxalate 242.23g is dissolved in 500mL toluene, was added drop-wise in four-hole boiling flask in 1 hour by normal pressure funnel subsequently.Dropwise rear continuation backflow three hours.Toluene distillation is complete, nitrogen replacement three times, and 1-2torr was decompressed in 20 minutes, also melt polymerization 4h, cooling obtain transparent products to be at this temperature warming up to 220 DEG C.After measured, its relative viscosity is 3.5, and glass transition temperature Tg is 50 DEG C, and saturated water absorption is 0.9%.
Embodiment 5
By trimethylhexamethylenediamine (2,2,4-and 2,4, the mixture of 4-position) 118.71g, 1,6-hexanediamine 29.05g and 500mL toluene joins in 2L four-hole boiling flask, replace nitrogen 3 times under mechanical stirring and system is warmed up to 60 DEG C. phenyloxalate 242.23g is dissolved in 500mL toluene, was added drop-wise in four-hole boiling flask in 1 hour by normal pressure funnel subsequently.Dropwise rear continuation backflow three hours.Toluene distillation is complete, nitrogen replacement three times, and 1-2torr was decompressed in 20 minutes, also melt polymerization 4h, cooling obtain transparent products to be at this temperature warming up to 220 DEG C.After measured, its relative viscosity is 4.5, and glass transition temperature Tg is 60 DEG C, and saturated water absorption is 1.8%.
Embodiment 6
By trimethylhexamethylenediamine (2,2,4-and 2,4, the mixture of 4-position) 150.37g, Putriscine 4.41g and 1000mL toluene join in 2L four-hole boiling flask, replace nitrogen 3 times under mechanical stirring and system is warmed up to 60 DEG C. in 1 hour, drip dibutyl oxalate 202.25g by normal pressure funnel subsequently.Dropwise rear continuation backflow three hours.Toluene distillation is complete, nitrogen replacement three times, and 2-3torr was decompressed in 20 minutes, also melt polymerization 4h, cooling obtain transparent products to be at this temperature warming up to 220 DEG C.After measured, its relative viscosity is 2.8, and glass transition temperature Tg is 63 DEG C, and saturated water absorption is 1.2%.
Embodiment 7
By trimethylhexamethylenediamine (2,2,4-and 2,4, the mixture of 4-position) 158.28g and 1000mL toluene joins in 2L four-hole boiling flask, replace nitrogen 3 times under mechanical stirring and system is warmed up to 60 DEG C, in 1 hour, dripping dibutyl oxalate 202.25g by normal pressure funnel subsequently.Dropwise rear continuation backflow three hours.Toluene distillation is complete, and nitrogen replacement three times, is warming up to 250 DEG C under nitrogen flowing and melt polymerization 4h, cooling obtain transparent products at this temperature.After measured, its relative viscosity is 2.7, and glass transition temperature Tg is 65 DEG C, and saturated water absorption is 1.1%.
Comparative example
By 1,12 diamino dodecane 200.36g and 500mL toluene join in 2L four-hole boiling flask, replace nitrogen 3 times under mechanical stirring and system is warmed up to 60 DEG C. and dripped in 1 hour after dibutyl oxalate 202.25g. dropwises by normal pressure funnel subsequently and continue backflow three hours.Toluene distillation is complete, nitrogen replacement three times, and 1-2torr was decompressed in 20 minutes, also melt polymerization 4h, cooling obtain opaque faint yellow solid to be at this temperature warming up to 220 DEG C.After measured, its relative viscosity is 3.2, and fusing point is 198 DEG C, and saturated water absorption is 0.9%.
Embodiment 1-9 monomer used and consumption as shown in table 1, each performance perameter of products obtained therefrom is as shown in table 2.
Table 1
Table 2
Claims (8)
1. a transparent nylon, is characterized in that, it contains branched-chain alkyl diamine unit and oxalic acid unit.
2. transparent nylon as claimed in claim 1, it is characterized in that, described branched-chain alkyl diamine unit is trimethylhexamethylenediamine unit.
3. transparent nylon as claimed in claim 1, is characterized in that, it is also the straight-chain aliphatic diamine unit of 4 ~ 12 containing carbonatoms, and the molar content of straight-chain aliphatic diamine unit in all diamine unit is 1 ~ 50mol%.
4. transparent nylon as claimed in claim 1, it is characterized in that, described oxalic acid unit comes from oxalate diester, be selected from dimethyl oxalate, oxalic acid diethyl ester, DPO, oxalic acid diisopropyl ester, dibutyl oxalate, di-isobutyl oxalate or oxalic acid di tert butyl carbonate any one or multiple.
5. transparent nylon as claimed in claim 1, it is characterized in that, with 95% sulfuric acid for solvent, working concentration is the relative viscosity that the transparent nylon solution of 0.01g/mL measures at 25 DEG C is 1.2 ~ 6.0.
6. a preparation method for the transparent nylon described in claim 1-5 any one, is characterized in that, comprises the following steps:
Step 1): at the temperature of inert gas and 30 DEG C-120 DEG C, diamine is slowly added in and joins in diamine in oxalate diester or by oxalate diester, react and obtain prepolymer after 2-6 hour; Wherein diamine is branched-chain alkyl diamines or branched-chain alkyl diamine mixture;
Step 2): under normal or reduced pressure, prepolymer melt polymerization is obtained transparent nylon product in 2-5 hour.
7. the preparation method of transparent nylon as claimed in claim 6, it is characterized in that, described branched-chain alkyl diamine unit is trimethylhexamethylenediamine unit.
8. the preparation method of transparent nylon as claimed in claim 6, is characterized in that, the mixture of described branched-chain alkyl diamine mixture to be trimethylhexamethylenediamine and carbonatoms the be straight-chain aliphatic diamines arbitrary proportion of 4 ~ 12.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111234207A (en) * | 2020-03-04 | 2020-06-05 | 东华大学 | Transparent bio-based polyamide and preparation method thereof |
| CN111691002A (en) * | 2020-06-23 | 2020-09-22 | 浙江恒澜科技有限公司 | Preparation method of high-strength low-modulus modified polyamide 56 industrial yarn |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1585796A (en) * | 2002-04-05 | 2005-02-23 | 三井化学株式会社 | Resin composition for light emitting diode reflectors |
| CN101541861A (en) * | 2006-12-11 | 2009-09-23 | 宇部兴产株式会社 | Polyamide resin |
| JP2015206003A (en) * | 2014-04-22 | 2015-11-19 | 宇部興産株式会社 | Polyamide resin and molded article produced by using the same |
-
2015
- 2015-11-26 CN CN201510837538.2A patent/CN105367785B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1585796A (en) * | 2002-04-05 | 2005-02-23 | 三井化学株式会社 | Resin composition for light emitting diode reflectors |
| CN101541861A (en) * | 2006-12-11 | 2009-09-23 | 宇部兴产株式会社 | Polyamide resin |
| JP2015206003A (en) * | 2014-04-22 | 2015-11-19 | 宇部興産株式会社 | Polyamide resin and molded article produced by using the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111234207A (en) * | 2020-03-04 | 2020-06-05 | 东华大学 | Transparent bio-based polyamide and preparation method thereof |
| CN111691002A (en) * | 2020-06-23 | 2020-09-22 | 浙江恒澜科技有限公司 | Preparation method of high-strength low-modulus modified polyamide 56 industrial yarn |
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