CN103965236B - A kind of polycarbonate chainextender and preparation method thereof - Google Patents

Abstract

The present invention relates to a kind of containing fluorenyl, polycarbonate chainextender and preparation method thereof containing silica structure.9,9-bis-(4-hydroxy ethoxy phenyl) fluorenes and diethyl dichlorosilane are prepared intermediate through condensation reaction, then to prepare the polycarbonate chainextender of epoxy group(ing) end-blocking through polycondensation with epoxy chloropropane.Invention introduces the rigidity fluorenes ring containing flexible side group and the siloxane bond with excellent flexibility, products therefrom both can significantly improve molecular weight and the second-order transition temperature of PC feed back, increase the melt strength of PC feed back, machine-shaping property can be improved again, further reduction internal stress, improve low-temperature impact resistance and flame retardant properties, and do not affect transparency.

Description

A kind of polycarbonate chainextender and preparation method thereof

Technical field

The present invention relates to a kind of polyester chain extender, specifically refer to a kind of containing fluorenyl, polycarbonate chainextender containing silica structure.

Background technology

Polycarbonate has good over-all properties and is widely used in multiple fields such as electric, building materials, automotive industry and packaging, but every annual meeting produces the PC dead meal of tens thousand of tons.Reclaiming as passed through, making full use of PC reworked material, development plastics recycling economy, not only can effectively alleviate social environment burden, economize on resources, be also the inevitable approach realizing the Sustainable development of PC industry.But because PC contains the ester bond of facile hydrolysis, after repeatedly reclaiming use, because the reasons such as thermo-oxidative ageing cause PC molecular weight and molecular weight comparatively large, yellowness index raises fast, and mechanical properties decrease is comparatively serious, and feed back use properties declines to a great extent.

For these reasons, PC chainextender is taken advantage of a situation and gives birth to.This type of chainextender is generally the styrene based copolymer containing epoxide group, acrylate group structure, and second-order transition temperature is lower, is generally 50 ~ 80 DEG C.In actual use procedure, extrusion equipment process operation temperature is general higher, usually can reach 180 ~ 280 DEG C.After this type of chainextender is added directly to forcing machine spout, realize dispersed before just produced reaction in local, define gel, also easily block opening for feed, cause formula uneven, produce unstable, result of use is had a greatly reduced quality.

Being the bisphenol compound that a class has Cardo ring skeleton structure containing fluorenes bisphenol cpd, is important monomer or the properties-correcting agent of the polycondensation products such as polycarbonate synthesis, epoxy resin, polyester or polyethers.Adopt and there is excellent thermotolerance and thermostability, high transparent, high refractive index, the characteristics such as lower photoelastic constant containing fluorenes bisphenol cpd modification gained polycarbonate, be widely used in the field such as aerospace, optical lens.Copolymeric siloxane polycarbonate has outstanding thermotolerance, weathering resistance and flame retardant properties, and low-temperature impact resistance is excellent, and processing forming is good.

Chinese patent literature CN103130982A proposes a kind of synthesis containing fluorenes high-temperature resistant silicone epoxy resin and curing, it adopts 9,9-bis-(4-hydroxyphenyl) fluorenes and dimethyldichlorosilane(DMCS) or diphenyl dichlorosilane prepare bisphenol fluorene/siloxane oligomer through condensation reaction, and prepare high-temperature-resistant epoxy resin through polycondensation based on this.Because 9,9-bis-(4-hydroxyphenyl) fluorenes belongs to rigid molecular structure, without flexible side group, greatly sterically hindered, in molecular chain, rotational resistance increases, and gained resin glass temperature significantly improves, but product fragility is large, applies limited.Though introduce the fragility that siloxane groups can improve epoxy resin to a certain extent, be limited to adopted dichlorosilane molecular structure, make totally to improve degree comparatively limited.

Summary of the invention

The object of this invention is to provide a kind of containing fluorenyl, polycarbonate chainextender and preparation method thereof containing silica structure, the defect that the molecular weight and molecular weight that solution regeneration PC causes because degrading causes over-all properties to decline to a great extent, obviously can improve mechanical property and the machine-shaping property of regeneration PC, improve its economic value added.

Object of the present invention is realized by following technical proposals: a kind of containing fluorenyl, preparation method containing the polycarbonate chainextender of silica structure, comprising:

(1) 9,9-bis-(4-hydroxy ethoxy phenyl) fluorenes, Isosorbide-5-Nitrae-dioxane are added in the reactor of nitrogen purging, removed under reduced pressure moisture after 65 DEG C of stirring 1h;

(2) diethyl dichlorosilane is added, feed rate 100ml/h, stir speed (S.S.) 150rpm, 70 DEG C of reaction 1.5h, logical nitrogen removes HCl gas, continues insulation reaction 3h, decompression extracts HCl gas, obtain 9,9-bis-(4-hydroxy ethoxy phenyl) fluorenes-diethylsilane-9,9-bis-(4-hydroxy ethoxy phenyl) fluorenes oligopolymer;

(3) in above-mentioned reactor, epoxy chloropropane, Tetrabutyl amonium bromide is added, stir speed (S.S.) 100-300rpm, reactor is metered into 50%NaOH solution after being warming up to 65 ~ 75 DEG C, 50%NaOH solution feed flow 50-200ml/h, feed time 2-4h, reduced-pressure backflow simultaneously, accumulative reaction times 3-5h, vacuum tightness 10-20kPa;

(4), after reaction terminates, the water in removed under reduced pressure reactor, epoxy chloropropane and Isosorbide-5-Nitrae-dioxane, at 130 ~ 160 DEG C, under vacuum tightness 0.5 ~ 1.0kPa condition, slough residual epoxy chloropropane and Isosorbide-5-Nitrae-dioxane through thin-film evaporator, obtain crude resin;

(5) in aftertreatment still, add deionized water, remaining 50%NaOH solution, 70 ~ 80 DEG C of insulations 2-3h, stir speed (S.S.) 200-400rpm, branch vibration layer, then add deionized water and repeatedly wash 3 times;

(6) resin solution after depickling process is at 140 ~ 170 DEG C, and slough Isosorbide-5-Nitrae-dioxane residual in resin through thin-film evaporator under vacuum tightness 0.5 ~ 1.0kPa condition, obtain product, its oxirane value is 0.15 ~ 0.20mol/100g,

The structural formula of product is as follows:

Polymerization degree n=0 ~ 0.5

Above-mentioned each material proportion is parts by weight, best material and proportioning as follows:

9,9-bis-(4-hydroxy ethoxy phenyl) fluorenes: 10

Diethyl dichlorosilane: 1.8

Isosorbide-5-Nitrae-dioxane: 50-100

Epoxy chloropropane: 12-20

Tetrabutyl amonium bromide: 0.4-0.8

50%NaOH solution: 2-5

Deionized water: 60-120.

In above-mentioned epoxy polycondensation technique of the present invention, catalyzer Tetrabutyl amonium bromide and NaOH both can effectively catalysis epoxy polycondensations, under the high temperature conditions, can cause epoxy group(ing) hydrolysis again simultaneously, cause target product oxirane value to decline, finally cause PC chain extending reaction activity to reduce.In order to reduce epoxy group(ing) hydrolysis probability, the present invention reduces the usage quantity of catalyzer Tetrabutyl amonium bromide in polycondensation unit, significantly improve solvent 1 simultaneously, the usage quantity of 4-dioxane and epoxy chloropropane, can effectively control reaction system viscosity in the condensation reaction later stage, thus ensure that target epoxide product has higher oxirane value.

The present invention utilizes target epoxide second-order transition temperature higher, is the characteristic of solid, at post-processing unit under normal temperature, direct employing deionized water and NaOH solution use, desolventize in conjunction with high-speed stirring depickling, easy and simple to handle, processing parameter is gentle, and practical effect is good.

The present invention adopts 9,9-bis-(4-hydroxy ethoxy phenyl) fluorenes, it belongs to two functional group's oxy-compound, owing to containing submissive ehter bond in molecule segment, relatively (9,9-bis-(4-hydroxyphenyl) fluorenes, its molecular chain kindliness is better, obviously can improve mechanical property and the processing rheological property of target product.Relative dimethyldichlorosilane(DMCS) or diphenyl dichlorosilane, the introducing of ethyl can further improve the kindliness of diethyl dichlorosilane molecular chain, improves processing rheological property.By arranging in pairs or groups use with 9,9-bis-(4-hydroxy ethoxy phenyl) fluorenes, can the molecular chain kindliness of active balance gained 9,9-bis-(4-hydroxy ethoxy phenyl) fluorenes/siloxane oligomer and resistance toheat.

The inventive method prepare containing fluorenyl, polycarbonate chainextender containing silica structure, due to introduce containing flexible side group rigidity fluorenes ring and there is the siloxane bond of excellent flexibility, this chainextender adds in PC reworked material can make polymer molecular chain again connect in the mode of straight chain, products therefrom both can significantly improve molecular weight and the second-order transition temperature of PC feed back, increase the melt strength of PC feed back, machine-shaping property can be improved again, further reduction internal stress, improve low-temperature impact resistance and flame retardant properties, and do not affect transparency.

Embodiment

Embodiment 1

1,1kg9,9-bis-(4-hydroxy ethoxy phenyl) fluorenes, 5kg Isosorbide-5-Nitrae-dioxane are added in the reactor of nitrogen purging, removed under reduced pressure moisture after 65 DEG C of stirring 1h;

2,0.18kg diethyl dichlorosilane is added, feed rate 100ml/h, stir speed (S.S.) 150rpm, 70 DEG C of reaction 1.5h, logical nitrogen removes HCl gas, continues insulation reaction 3h, decompression extracts HCl gas, obtain 9,9-bis-(4-hydroxy ethoxy phenyl) fluorenes-diethylsilane-9,9-bis-(4-hydroxy ethoxy phenyl) fluorenes oligopolymer;

3, in above-mentioned reactor, add 1.2kg epoxy chloropropane, 40g Tetrabutyl amonium bromide, stir speed (S.S.) 300rpm, reactor is metered into total amount after being warming up to 65 DEG C be 0.5kg 50%NaOH solution.50%NaOH solution feed flow 100ml/h, feed time 3h, simultaneously reduced-pressure backflow.Accumulative reaction times 4h, vacuum tightness 10kPa;

4, after reaction terminates, the water in 10kPa removed under reduced pressure reactor, epoxy chloropropane and Isosorbide-5-Nitrae-dioxane, at 130 DEG C, under vacuum tightness 1.0kPa condition, slough residual epoxy chloropropane and Isosorbide-5-Nitrae-dioxane through thin-film evaporator, obtain crude resin;

5, in aftertreatment still, add 3kg deionized water, remaining 50%NaOH solution, stir speed (S.S.) 200rpm, 70 DEG C of insulation 2h, branch vibration layer, then add 9kg deionized water in batches and repeatedly wash 3 times;

6, de-acid-treated resin solution is at 140 DEG C, and slough organic solvent residual in resin through thin-film evaporator under vacuum tightness 0.5kPa condition, obtain product, oxirane value is 0.17mol/100g.

Embodiment 2

Raw material composition and reaction process parameter are as table 1, and products obtained therefrom oxirane value is 0.18mol/100g.

Embodiment 3

Raw material composition and reaction process parameter are as table 1, and products obtained therefrom oxirane value is 0.15mol/100g.

Embodiment 4

Raw material composition and reaction process parameter are as table 1, and products obtained therefrom oxirane value is 0.17mol/100g.

Embodiment 5

Raw material composition and reaction process parameter are as table 1, and products obtained therefrom oxirane value is 0.20mol/100g.

Embodiment 6

Raw material composition and reaction process parameter are as table 1, and products obtained therefrom oxirane value is 0.19mol/100g.

Embodiment 7

Raw material composition and reaction process parameter are as table 1, and products obtained therefrom oxirane value is 0.18mol/100g.

Embodiment 8

Raw material composition and reaction process parameter are as table 1, and products obtained therefrom oxirane value is 0.19mol/100g.

Comparative example 1(and embodiment 1 contrast)

9-bis-(4-hydroxy phenyl) fluorenes is adopted to replace 9-bis-(4-hydroxy ethoxy phenyl) fluorenes, dimethyldichlorosilane(DMCS) replaces diethyl dichlorosilane consumption, both proportioning raw materials are constant, all the other supplementary materials composition and reaction parameter are with embodiment 1, and products obtained therefrom oxirane value is 0.20mol/100g.

Comparative example 2(and embodiment 2 contrast)

9-bis-(4-hydroxy phenyl) fluorenes is adopted to replace 9-bis-(4-hydroxy ethoxy phenyl) fluorenes, diphenyl dichlorosilane replaces diethyl dichlorosilane consumption, both proportioning raw materials are constant, all the other supplementary materials composition and reaction parameter are with embodiment 1, and products obtained therefrom oxirane value is 0.17mol/100g.

Comparative example 3(and embodiment 3 contrast)

Isosorbide-5-Nitrae-dioxane consumption is adjusted downward to 4kg, and epoxy chloropropane consumption is adjusted downward to 1.0kg, and the stir speed (S.S.) of step 3 is increased to 300rpm, and reaction process is as table 2, and products obtained therefrom oxirane value is 0.08mol/100g.

Table 1

Comparative example 4(and embodiment 4 contrast)

Tetrabutyl amonium bromide consumption is adjusted downward to 30g, and 50%NaOH solution usage is increased to 0.6kg, and the NaOH flow in step 3 is increased to 100ml/h, and reaction process is as table 2, and products obtained therefrom oxirane value is 0.12mol/100g.

Comparative example 5(and embodiment 5 contrast)

Tetrabutyl amonium bromide consumption is increased to 100g, and the temperature of reaction in step 3 drops to 60 DEG C, and the accumulative reaction times is increased to 7h, and reaction process is as table 2, and products obtained therefrom oxirane value is 0.14mol/100g.

Comparative example 6(and embodiment 6 contrast)

Isosorbide-5-Nitrae-dioxane consumption is increased to 12kg, and the accumulative reaction times in step 3 is increased to 7h, and reaction process is as table 2, and products obtained therefrom oxirane value is 0.09mol/100g.

Comparative example 7(and embodiment 7 contrast)

Epoxy chloropropane consumption is increased to 2.5kg, and the stir speed (S.S.) in step 3 drops to 50rpm, and the stir speed (S.S.) in step 5 drops to 100rpm, and reaction process is as table 2, and products obtained therefrom oxirane value is 0.11mol/100g.

Comparative example 8(and embodiment 8 contrast)

The total consumption of deionized water is increased to 15kg, and the vacuum tightness in step 3 is increased to 30kPa, and devolatilization vacuum tightness drops to 0.2kPa, and reaction process is as table 2, and products obtained therefrom oxirane value is 0.12mol/100g.

From comparative example, 9-bis-(4-hydroxy phenyl) fluorenes is adopted directly to replace 9-bis-(4-hydroxy phenyl) fluorenes, and react with dimethyldichlorosilane(DMCS) or diphenyl dichlorosilane and also can obtain corresponding product product, but under existing processing condition, reactive behavior is relatively low, and product oxirane value is lower than theoretical value.

1,4-dioxane and epoxy chloropropane total amount lower when, lower further the dispersion that its consumption is unfavorable for raw material and epoxidation reaction product, thus suppress the carrying out of epoxidation reaction, impel product oxirane value to decline to a great extent, finally cause the chain extension deleterious of product.But significantly excessive Isosorbide-5-Nitrae-dioxane and epoxy chloropropane do not improve the oxirane value of product, and add the load of reduced vacuum on the contrary, energy consumption significantly increases.Though the raising of basic catalyst Tetrabutyl amonium bromide and sodium hydroxide solution consumption can promote epoxidation reaction, the phase is unfavorable for ring-closure reaction after the reaction, causes the oxirane value of the finished product to decline to a great extent.Relative sodium hydroxide, basic catalyst Tetrabutyl amonium bromide is more conducive to the carrying out of epoxidation reaction.

Base catalysis epoxidation reaction should keep suitable stir speed (S.S.), so that reaction solution and catalyzer is dispersed, the reaction later stage particularly significantly increased in viscosity seems particularly important.Reaction times can not be long, otherwise easily initiation hydrolysis causes oxirane value to decline.The reduced vacuum degree of epoxidation stage is low as far as possible, removes the water that epoxy chloropropane open loop generates in time, otherwise can suppress the carrying out of epoxidation reaction.

Embodiment 1, embodiment 3, embodiment 5, embodiment 7, comparative example 1, comparative example 2, comparative example 5, comparative example 7 are applied to the manipulation of regeneration of PC feed back, its addition is that every 100 weight part PC feed backs add 0.5 weight part chainextender, after high-speed mixing, being directly injection molded into standard batten by standard size carries out various performance test, the physicals of standard batten is all by ASTM standard testing, testing method is as shown in table 3, and test result is as shown in table 4.

Table 2

Table 3 performance test methods

Performance	Testing method	Condition
			Room temperature Izod notch shock	ASTM D256	3.2mm，23℃
Low temperature Izod notch shock	ASTM D256	3.2mm，-30℃
			Tensile strength	ASTM D638	3.2mm，50mm/min
Elongation at break	ASTM D638	3.2mm，50mm/min
			Mass flow rate	ASTM D1238	300℃/1.2kg
Heat-drawn wire	ASTM D648	1.82MPa
			Transmittance	ASTM D1003	1mm

Table 4 the performance test results

Performance	PC feed back	Embodiment 1	Embodiment 3	Embodiment 5	Embodiment 7	Comparative example 1	Comparative example 2	Comparative example 5	Comparative example 7
										Room temperature Izod notch shock, J/m	455	580	520	640	550	510	485	560	496
Low temperature Izod notch shock, J/m	90	130	110	155	114	100	90	96	94
										Tensile strength, MPa	55	57	56	58	56	57	55	57	55
Elongation at break, %	70	85	80	90	83	75	70	85	74
										Mass flow rate, g/10min	20	15	17	10	16	10	13	15	18
Heat-drawn wire, DEG C	123	124	124	126	124	124	124	124	123
										Transmittance, %	80	81	81	84	81	81	78	82	79
Chainextender oxirane value, mol/100g		0.17	0.18	0.20	0.18	0.20	0.17	0.14	0.11

From table 4 performance test data, the inventive method prepare containing fluorenyl, good containing the polycarbonate chainextender result of use of silica structure, the over-all properties obviously can improving feed back is on a small quantity added in PC feed back, room-temperature impact strength significantly improves, low temperature impact strength doubles, and heat-drawn wire and transmittance all have small size raising.

9,9-bis-(4-hydroxy ethoxy phenyl) fluorenes is owing to containing submissive ehter bond in molecule segment, and (9,9-bis-(4-hydroxyphenyl) fluorenes, its molecular chain kindliness is better relatively.Relative dimethyldichlorosilane(DMCS) or diphenyl dichlorosilane, the introducing of ethyl can further improve the kindliness of diethyl dichlorosilane molecular chain, improves processing rheological property.By arranging in pairs or groups use with 9,9-bis-(4-hydroxy ethoxy phenyl) fluorenes, can the machine-shaping property of active balance gained 9,9-bis-(4-hydroxy ethoxy phenyl) fluorenes/siloxane oligomer, mechanical property and resistance toheat.Comparing embodiment 1 and comparative example 1, comparative example 2 are known, and under the prerequisite ensureing product mechanical property, the feed back PC mobility in embodiment 1 is better, but mechanical property, thermal characteristics conservation rate are good.

Claims (3)

1. the preparation method of a polycarbonate chainextender, it is characterized in that: comprise the following steps: (1) is by 9,9-bis-(4-hydroxy ethoxy phenyl) fluorenes, Isosorbide-5-Nitrae-dioxane add in the reactor of nitrogen purging, removed under reduced pressure moisture after 65 DEG C of stirring 1h; (2) diethyl dichlorosilane is added, feed rate 100ml/h, stir speed (S.S.) 150rpm, 70 DEG C of reaction 1.5h, logical nitrogen removes HCl gas, continues insulation reaction 3h, decompression extracts HCl gas, obtain 9,9-bis-(4-hydroxy ethoxy phenyl) fluorenes-diethylsilane-9,9-bis-(4-hydroxy ethoxy phenyl) fluorenes oligopolymer; (3) in above-mentioned reactor, epoxy chloropropane, Tetrabutyl amonium bromide is added, stir speed (S.S.) 100-300rpm, reactor is metered into 50%NaOH solution after being warming up to 65 ~ 75 DEG C, 50%NaOH solution feed flow 50-200ml/h, feed time 2-4h, reduced-pressure backflow simultaneously, accumulative reaction times 3-5h, vacuum tightness 10-20kPa; (4), after reaction terminates, the water in removed under reduced pressure reactor, epoxy chloropropane and Isosorbide-5-Nitrae-dioxane, at 130 ~ 160 DEG C, under vacuum tightness 0.5 ~ 1.0kPa condition, slough residual epoxy chloropropane and Isosorbide-5-Nitrae-dioxane through thin-film evaporator, obtain crude resin; (5) in aftertreatment still, add deionized water, remaining 50%NaOH solution, 70 ~ 80 DEG C of insulations 2-3h, stir speed (S.S.) 200-400rpm, branch vibration layer, then add deionized water and repeatedly wash 3 times; (6) resin solution after depickling process is at 140 ~ 170 DEG C, and slough Isosorbide-5-Nitrae-dioxane residual in resin through thin-film evaporator under vacuum tightness 0.5 ~ 1.0kPa condition, obtain product, its oxirane value is 0.15 ~ 0.20mol/100g; The structural formula of product is as follows:

Polymerization degree n=0-0.5.

2. the preparation method of polycarbonate chainextender according to claim 1, is characterized in that: each material proportion is parts by weight, concrete material and proportioning as follows:

9,9-bis-(4-hydroxy ethoxy phenyl) fluorenes: 10

Diethyl dichlorosilane: 1.8

Isosorbide-5-Nitrae-dioxane: 50-100

Epoxy chloropropane: 12-20

Tetrabutyl amonium bromide: 0.4-0.8

50%NaOH solution: 2-5

Deionized water: 60-120.

3. a polycarbonate chainextender as claimed in claim 2, its structural formula is:

Polymerization degree n=0-0.5.