CN1061665C - Cast epoxy resin for high-voltage switch and its preparation - Google Patents

Abstract

The present invention discloses a cast epoxy resin for a high-voltage switch and a preparation method thereof. Bisphenol A and epoxy chloropropane are used as principal raw materials, and epoxyalkane containing an epoxy group and epoxy chain hydrocarbon are used as improver. A resin intermediate is synthesized in advance, and then, a resin product with an epoxy value of 0.20 to 0.28 eq/100g is synthesized under the function of catalyst. The present invention solves the problems of poor high-voltage resistance, low mechanical strength, poor casting quality, etc. of a high-voltage resistant element which is cast by an addition method in the prior art. The present invention has the advantages of low resin viscosity of the product, stable high-voltage resistance and dimension of a casting, good quality, high physical property, high mechanical property, etc., and the present invention can be widely used for casting various high-voltage resistant electrical apparatus.

Description

A kind of high-tension switch casting epoxy resin and manufacture method thereof

The present invention relates to a kind of high-tension switch casting epoxy resin and manufacture method thereof, especially a kind of SF6 high-tension switch casting epoxy resin and manufacture method thereof.

In the prior art, existing many high-tension switchs report of Resins, epoxy, U.S. Pat 4780360 has been reported a kind of high pressure SF that is used for of Siemens Company ₆The preparation method of the Resins, epoxy of switch comes the modified bisphenol A based epoxy resin with PET or aromatic hydrocarbons polyamine, makes the anionoid polymerization solidifying agent with uncle's aryl diamine, and Japanese Patent J86011408 and 86011407 has reported a kind of high pressure SF ₆The switch insulating material, this isolator is made up of the epoxy resin ingredient of 100pts.wt and the aluminum oxide of 200～500ptswt, epoxy resin ingredient comprises the glycidyl-3-(2-glycidyl)-5 of the bisphenol A type epoxy resin and 25%～55% (wt) of 75%～45% (wt) again, the two methyl glycolylurea resins of 5-; German patent DE 2810035 has been reported and has been used for SF ₆High-voltage switch gear epoxy resin ingredient, this component are with white clouds masonrys weighting agent, make the operation auxiliary agent with the lower aliphatic alcohols that is higher than six carbon, two hydroxy fatty alcohols etc. of being higher than five carbon, add dihydroxyphenyl propane based epoxy resin composition again.These resins are mostly with alicyclic epoxide compound or contain the epoxy resin component modification of alicyclic ring, because of what adopt is additive process, so cost is high and operation inconvenience, such domestic resin property is poor, as the casting dimension instability, easily produce bubble, easily be full of cracks, thereby it is poor to satisfy the requirement and the casting quality of pouring technology.

The object of the present invention is to provide a kind of high-tension switch casting epoxy resin and manufacture method thereof, its product viscosity is suitable, shrinking percentage is little and internal stress is little, and is high and high pressure resistant by the casting strength of this production, long service life.

In order to achieve the above object, the present invention has adopted following technical scheme: prepare resin of the present invention with dihydroxyphenyl propane, epoxy chloropropane and properties-correcting agent as main raw material, mixture with one or more arbitrary proportions of the oxirane ring alkane that contains epoxy group(ing), epoxy chain hydrocarbon is made properties-correcting agent, reaction process: (1) synthetic resins intermediate: the component of resin intermediate and proportioning (mol) are: epoxy chloropropane 6.0～9.0; Caustic alkali 1.9～2.5; Properties-correcting agent 0.4～1.5; Dihydroxyphenyl propane 1.0.Carry out according to the following steps: A, by being metered into dihydroxyphenyl propane, the caustic alkali of properties-correcting agent and total amount 3%～4% is in reactor, the catalyst etherifying reaction is 3 hours under 60 ± 3 ℃ temperature, B then, by the caustic alkali that is metered into epoxy chloropropane and total amount 75%～80%, 66 ± 3 ℃ temperature and-0.080～-vacuum tightness of 0.085MPa under reaction 2 hours, dewater dihydroxyphenyl propane chloropharin body, reclaim epoxy chloropropane, the toluene dissolving, C then, add surplus caustic alkali, reaction is 1 hour under 85～88 ℃ temperature, getting oxirane value is the low-molecular-weight resin of 0.42～0.53eq/100g, desalination, washing, reclaim toluene, (2) synthetical resin products again: by dihydroxyphenyl propane: resin intermediate is 0.15-0.28: 1.0, and catalyzer: dihydroxyphenyl propane is that 0.0005～0.0020: 1.0 (being weight ratio) add dihydroxyphenyl propane and catalyzer in resin intermediate, reaction is 2 hours under 140～150 ℃ temperature, and getting oxirane value is the rosin products of 0.20～0.28eq/100g; Described catalyzer is the mixture of one or more arbitrary proportions of quaternary ammonium salt and quaternary phosphonium salt.

In implementing process of the present invention, at first should control the consumption of epoxy chloropropane well, mol ratio with epoxy chloropropane and dihydroxyphenyl propane is 6.0～9.0: 1.0 are advisable, the consumption of epoxy chloropropane is not too high or too low, if the consumption of epoxy chloropropane is low excessively, then formed resin intermediate oxirane value is on the low side, thereby influence the physical and mechanical properties of finished product casting resin, the oxirane value of product is along with the ratio of epoxy chloropropane to dihydroxyphenyl propane increases and improves, but when its ratio is too high, then the increase trend of oxirane value is gradually mild, thereby there is no need to add too much epoxy chloropropane; In the enforcement, used caustic alkali can be sodium hydroxide or potassium hydroxide, but generally all adopt inexpensive sodium hydroxide, its consumption mainly influences the hydrolyzable chlorine content of resin intermediate, oxirane value and cause epoxy chloropropane, the hydrolysis of the epoxy group(ing) of Resins, epoxy, thereby influence resin quality and raw materials consumption, increase with oxygen sodium oxide amount, Resins, epoxy hydrolyzable chlorine content reduces, oxirane value increases, but the amount of working as sodium hydroxide is excessive, then cause the epoxy group(ing) hydrolysis of Resins, epoxy, thereby reduce the resin epoxy group content or cause epoxy ring-opening and polymerization, causing the molecular resin quantitative change is greatly that viscosity increases; In addition, epoxy chloropropane consumption excessive in the system increases, and has improved the resin cost.Therefore, must be with sodium hydroxide: the molar ratio of dihydroxyphenyl propane be controlled at 1.9～2.5: in 1.0 the scope.The mode that sodium hydroxide preferably adopts aforementioned substep to add preferably slowly adds when the existing epoxy chloropropane of reaction system, and it is good especially to add sodium hydroxide in the dropping mode, is easy to control reaction temperature like this.In the enforcement, behind the synthetic resins intermediate, continue to add dihydroxyphenyl propane to adjust finished product molecular resin amount, the consumption of dihydroxyphenyl propane is wanted suitably, be controlled at dihydroxyphenyl propane: intermediate is 0.15～0.28: 1.0 better, and this moment, resin viscosity, foundry goods physical and mechanical properties and thermal characteristics were all comparatively desirable.

The present invention's technical scheme preferably can be: the add-on of properties-correcting agent is wanted suitably, the mol ratio of properties-correcting agent and dihydroxyphenyl propane is preferably in 0.6～0.8: in 1.0 the scope, but generally can be: select for use in 1.0 the scope 0.4～1.5, the properties-correcting agent consumption too greatly then surpasses response capacity, causes unnecessary waste; The properties-correcting agent consumption is low excessively, does not then have and adjusts the Resins, epoxy composition, changes the product activity to improve the purpose of casting strength.Properties-correcting agent of the present invention can be selected for use in the wide range that contains the oxirane ring alkane of epoxy group(ing), epoxy chain hydrocarbon, can use the mixture of any or several arbitrary proportions in this two compounds, all can play the ideal effect, for example oxyethane, propylene oxide, oxirane ring propane and epoxy-cyclohexane etc., but preferably adopt epoxy cyclohexane and propylene oxide a kind of or its mixture wherein, its reaction effect is good and raw material is cheap and easy to get.

The present invention's technical scheme preferably can also be: add appropriate amount of catalysts during synthetical resin products, catalyzer can use general formula to be X (R in the formula ₁～R ₄Can distinguish C ₁～C ₈Alkyl, X is Cl, Br or I) quaternary ammonium salt, general formula be X (R in the formula ₁～R ₄Can distinguish or simultaneously for C ₁～C ₈Alkyl, phenyl, X is Cl, Br or I) one or more mixtures of quaternary alkylphosphonium salt, tetramethyl ammonium chloride for example, trimethylammonium ethyl ammonium iodide, triphenyl tetrabutyl phosphonium bromide phosphorus or tetra-tert ammonium chloride etc., catalyst consumption is wanted suitably, the amount that adds catalyzer during synthetical resin products is with catalyzer: dihydroxyphenyl propane is that 0.0005～0.0020: 1.0 (weight) are calculated as suitable, catalyst levels is very big to the influence of rosin products, when the ratio of catalyzer and dihydroxyphenyl propane is lower than certain value, reaction conversion ratio and catalyst levels positive correlation, continue to increase again catalyst levels then the reaction conversion rate increase slow down, have little significance.In specific implementation process, preferentially select tetramethyl ammonium chloride, triphenylbut positive group bromo-phosphonium for use, with wherein any or they arbitrary proportion mixture all can, its excellent catalytic effect, raw material is cheap and easy to get.

The present invention's technical scheme preferably also can be: the zinc powder that adds dihydroxyphenyl propane weight 0.2 ‰～0.7 ‰ in catalyst etherifying reaction process (1) A; zinc powder is main as reductive agent in reaction system; it is comparatively active easily by airborne oxygen institute's oxidation and painted material to play a part protection; so that the color and luster of control sold resin; the zinc powder consumption is crossed the effect that does not have the control color and luster at least and is caused product color dark; also there is no need to add too much, in order to avoid cause waste.

Compared with prior art, the present invention has following tangible advantage:

1, rosin products viscosity is low, and working life is suitable, is particularly suitable for cast and uses, and respond well by the following technical recipe and the processing condition casting of Huatong Switch Factory, Shanghai: filling a prescription is Resins, epoxy: phthalic anhydride: filler (300 order SiO ₂Powder)=1: 0.35: 2 (weight), processing condition are 120 ± 2 ℃/2 hours, 130 ± 2 ℃/1 hour, and 140 ± 2 ℃/12 hours.

2, product is high pressure resistant, anti-SF ₆Degradation production, the foundry goods long service life.By K * 5720.02g boxlike insulator among the technical recipe casting ZF-110K of Huatong Switch Factory, Shanghai; three products are tested result such as table 1: table 1: electric performance test result by the component electromechanical properties of carrying out of amount component technology condition K * 0587031 defined of GIS product

Test subject	Desired value	Measured value	Differentiate	Test condition
					I is proof voltage frequently	250KV/5min does not have flashover, punctures	265KV/5min	Qualified	Fill with SF in the closed jar 6Gas is the external insulation medium, and gaseous tension is 0.3MPa.
Impact voltage-withstand	195KV ± 3 time nothing punctures flashover	190KV/t5 time	Qualified
				Partial discharge quantity	Under the 80KV less than 5PC	0.4PC under the 80KV	Qualified
Water pressure resistance test recessed to	1.7MPa/min do not have sound and damage	2.0MPa/min 2.5MPa/min	Qualified
				Protruding to	2.5MPa/min do not have sound and damage	3.0MPa/min 3.5MPa/min	Qualified

Above technology and application test result show: the quality index of rosin products meets the processing requirement of corresponding high-voltage switch gear T.

3, internal stress is little, and the product casting dimension is stable, and shrinking percentage is little, and foundry goods is smooth smooth, and the surface does not have be full of cracks and pore, the casting strength height, and quality is good.

Table 2 is that Xi'an High-tension Switch Factory is found when making the boxlike insulator of this resin-cast 220KV, its cast gate place is that flat its cast gate with other poured with epoxy resin then has very dark depression basically, this has proved that just products solidifying thing shrinkability of the present invention is little, detect the linear expansivity under the differing temps, this product is all little than AralcliteB41, and this point also has been described.

Linear expansivity (* 10 under table 2 differing temps ^-6K ^-1)

Temperature	This product	B41
			20	28．0	33．5
30	42．3	46．0
			40	56．2	62．5
50	62．8	69．4
			60	65．9	73．7
70	67．8	75．1
			80	71．5	78．9
90	76．4	91．6
			100	86．1	128．0

Table 3 is by the foundry goods over-all properties contrast table of the B-41 resin of the product of the present invention of the explained hereafter of embodiment 1～3 and Switzerland Ciba-Geigy company (Huatong Switch Factory, Shanghai's test).

Table 3 foundry goods over-all properties contrast table

Test subject	Unit	Desired value	Example 1 resin	Example 2 resins	Example 3 resins	B-41	Test conditions	Standard
									Viscosity	MPa·s	380 ～520	400	410	410	380	120 ℃ of constant temperature	GB12007.4-89
The viscosity rate of rise	％	≤10	11.4	10.9	10.9	12.1	120℃/24h
									Softening temperature	℃	45-55	51	52	52	51	Ring and ball method	GB12007.4-89
Fugitive constituent	％	≤0.5	0.15	0.09	0.12	0.1	130℃/2h	G86740-84
									Pot life	min	70-110	99	98	91	101	120±2℃
Tensile strength	MPa	70-90	66.9	73.2	65.2	70.3		ISO/R527
									Bending strength	MPa	100-120	102	115	144	144		ISO/R178
Shock strength	KJ/m 2		16.7	25.5	26.5	23.8
									Proportion	g/cm 3	1.15 -1.20	1.24	1.24	1.23	1.23
Water-intake rate	％		0.03	0.07	0.04	0.03	Immersion 24h
									Surface resistivity	MΩ		2.9×108	2×109	6.5×108	1.7×109
Volume specific resistance	MΩ.M		4.9×108	2.4×108	5.9×108	2.7×108
									Dielectric strength	MV/m		31	28	26	29
Shrinking percentage	％		1.25	1.25	1.35	1.24
									Dielectric loss angle tangent			0.032	0.033	0.030	0.030

Below by specific embodiment embodiments of the present invention are described in further detail:

Embodiment 1

At volume is 1000ml, is furnished with thermometer, agitator, add 1mol (228g) dihydroxyphenyl propane in the four-hole boiling flask of reflux exchanger, 0.5mol (29g) cycloalkanes propane, 0.06mol concentration is 45% NaOH (5.3g) solution, 0.1g zinc powder, be warming up to 60 ℃ after being heated to 55 ℃ voluntarily, reaction is 3 hours under this temperature, reaction mixture moved to the backflow phase splitter is housed, thermometer, the volume of agitator and dropping funnel is in the four-hole boiling flask of 1000ml, and the epoxy chloropropane (566g) of adding 6.0mol98%, NaOH (142g) solution that in dropping funnel, adds 1.6mol concentration 45%, at the uniform velocity drip in 2 hours, at 66 ± 3 ℃, pressure reacts under-0.082MPa the vacuum tightness, epoxy chloropropane and water form azeotrope, constantly from reactor, steam and phase-splitting in phase splitter, the epoxy chloropropane of lower floor is back in the reactor water on venting upper strata in the phase splitter; Keep 66 ± 3 ℃ of temperature of reaction after NaOH drips, vacuum tightness-0.082MPa half an hour, reaction is carried out fully; Be warming up to 100 ℃ gradually, dehydration, again gradually gas clean-up to≤-0.098MPa, be warming up to 100 ℃, decylization oxygen chloropropane is about half an hour, and system is cooled to below 100 ℃ after replying normal pressure, add 285ml toluene and make solvent, the NaOH that adds 0.30mol15% adjusts the temperature to about 85 ℃ and reacted 1 hour, adds 350ml toluene again and makes solvent; Add water 100ml and stirred 5 minutes, leave standstill after 30 minutes and remove lower layer of water, add an amount of 10%H ₃PO ₄Being neutralized to reactant PH is 7, stirs, and removes lower layer of water behind the standing demix, and reaction mixture is warming up to 160 ℃, be decompressed to-0.098MPa piptonychia benzene half an hour, the 286g resin intermediate, oxirane value is 0.45eq/100g.

With resin intermediate 200g, dihydroxyphenyl propane 35.2g mouth is to the four-hole boiling flask that thermometer, reflux exchanger, agitator are housed, add 17.6 milligrams of catalyzer tetramethyl ammonium chlorides, reaction is 2 hours under 140～150 ℃ temperature, get the 255g epoxy resin product, oxirane value is 0.205eq/100g.

Embodiment 2～8

Working method is with example 1, and processing condition are with example 1, and raw material ratio, resin intermediate and final resin oxirane value see Table 4.

Table 4 material proportion table

The real-valued example of executing of number of steps	Synthetic low-molecular-weight resin intermediate (1)							Sintetics		Product oxirane value eq/100g
											A			B		C		(2)
	Dihydroxyphenyl propane mol	Properties-correcting agent mol	NaOH mol	ECH mol	NaOH mol	NaOH mol	Oxirane value eq/100g	Dihydroxyphenyl propane: intermediate	Catalyzer: dihydroxyphenyl propane
											1	1.0	0.1(1)	0.06	6.0	1.6	0.30	0.45	0.16	0.5(1)	0.205
2	1.0	1.0(2)	0.08	7.2	1.8	0.43	0.51	0.25	1(2)	0.265
											3	1.0	1.5(3)	0.07	8.0	1.9	0.35	0.50	0.27	2(3)	0.272
4	1.0	0.8(4)	0.057	8.5	1.45	0.285	0.42	0.20	0.8(4)	0.208
											5	1.0	1.2(1+2)	0.1	9.0	1.75	0.55	0.52	0.18	1.2(2)	0.260
6	1.0	0.75(1+3)	0.065	6.5	2.00	0.50	0.47	0.24	1.4(1)	0.241
											7	1.0	1.45(2)	0.095	7.5	1.65	0.47	0.48	0.26	1(1)	0.267
8	1.0	0.6(1)	0.075	8.2	1.92	0.40	0.53	0.23	1.5(2)	0.264

Annotate:

1, the numeral 1 in () is shown propylene oxide in the properties-correcting agent hurdle, and 2 show epoxy cyclohexane, and 3 show oxyethane, and 4 show oxirane ring propane.

2, the numeral 1 in () is a tetramethyl ammonium chloride in the catalyst column, and 2 show triphenyl tetrabutyl phosphonium bromide phosphorus, and 3 show tetra-tert phosphorus chloride, and 4 show trimethylammonium ethyl ammonium iodide.Catalyzer in this hurdle: the value of dihydroxyphenyl propane is a weight ratio, and its unit is a thousandth, shows 0.5 ‰ as 0.5.

3, dihydroxyphenyl propane: intermediate is a weight ratio.

Claims (5)

1, a kind of high-tension switch manufacture method of casting epoxy resin, earlier synthetic low-molecular-weight resin intermediate, synthetical resin products under catalyst action then, the invention is characterized in: the mixture with one or more arbitrary proportions of the oxirane ring alkane, the epoxy chain hydrocarbon that contain epoxy group(ing) is made properties-correcting agent, and reaction process comprises:

(1) synthetic resins intermediate:

The component of resin intermediate and proportioning (mol ratio) are:

Epoxy chloropropane 6.0～9.0

Caustic alkali 1.9～2.5

Properties-correcting agent 0.4～1.5

Dihydroxyphenyl propane 1.0

Carry out according to the following steps:

A, by the caustic alkali that is metered into dihydroxyphenyl propane, properties-correcting agent and total amount 3%～4% in reactor, catalyst etherifying reaction is 3 hours under 60 ± 3 ℃ temperature, then

B, by the caustic alkali that is metered into epoxy chloropropane and total amount 75%～80%, 66 ± 3 ℃ temperature and-0.080～-vacuum tightness of 0.085MPa under reaction 2 hours, dewater dihydroxyphenyl propane chloropharin body, reclaim epoxy chloropropane, the toluene dissolving, then

C, adding surplus caustic alkali, reaction is 1 hour under 85～88 ℃ temperature, and getting oxirane value is the low-molecular-weight resin of 0.42～0.53eq/100g, desalination, washing is reclaimed toluene, again

(2) synthetical resin products:

By dihydroxyphenyl propane: resin intermediate is 0.15～0.28: 1.0, catalyzer: dihydroxyphenyl propane is that 0.0005～0.0020: 1.0 (being weight ratio) add dihydroxyphenyl propane and catalyzer in resin intermediate, reaction is 2 hours under 140～150 ℃ temperature, and getting oxirane value is the rosin products of 0.20～0.28eq/100g;

Described catalyzer is the mixture of one or more arbitrary proportions of quaternary ammonium salt and quaternary phosphonium salt.

2, manufacture method according to claim 1 is characterized in that: the mol ratio of properties-correcting agent and dihydroxyphenyl propane is 0.6～0.8 in the synthetic resins intermediate (1): 1.0.

3, manufacture method according to claim 1 is characterized in that: properties-correcting agent is epoxy cyclohexane, propylene oxide.

4, manufacture method according to claim 1 is characterized in that: the catalyzer that synthetical resin products process (2) adopts is tetramethyl ammonium chloride, triphenyl normal-butyl bromination phosphorus.

5, manufacture method according to claim 1 is characterized in that: catalyst etherifying reaction process (1) A adds the zinc powder of dihydroxyphenyl propane weight 0.2 ‰～0.7 ‰.