CN1208049A - Diethenyl benzene used for ion exchange resin - Google Patents

Abstract

The divinyl benzene for ion exchange resin has reasonable components including diethyl benzene 2-10%; that for gel resin has one DVB content of 48-52%, one ratio of p-DVB to m-DVB being 1 to 2-2.3 and one naphthalene content lower than 1%; and that for macroporous resin has one DVB content of 58-62%, one ratio of p-DVB to m-DVB being 1 to 1.8-2.0 and one naphthalene content lower than 1.5%. The present invention can raise the first-grade product rate of IER, raise its after-milling sphericity and stabilize its production process.

Description

The divinylbenzene that is used for ion exchange resin

The present invention relates to topmost cross linking agent divinylbenzene in the ion exchange resin production.

The topmost purposes of divinylbenzene (hereinafter to be referred as DVB) is the manufacturing that is used for ion exchange resin (hereinafter to be referred as IER) in the organic synthesis material.DVB IER in play interlinkage, adjust the vital role of mechanical strength of resin, exchange capacity, moisture etc.It is made through technologies such as catalytic dehydrogenation, rectifying by diethylbenzene, has 8 kinds of components (comprising isomers): p-DVB, m-DVB, p-diethylbenzene, m-diethylbenzene, p-ethyl styrene, m-ethyl styrene, naphthalene, triethyl-benzene.Except that DVB, other component is that raw material brings or pay reaction product.Standard one standard No. of the industrial divinylbenzene of People's Republic of China (PRC) petroleum chemical industry issue is SH/T1485.1-95, to the specification of quality of divinylbenzene is:

Project	????DVB45			????DVB55			Test method
								Excellent	First-class	Qualified	Excellent	First-class	Qualified
	Outward appearance	Colourless or light yellow transparent liquid												Range estimation
Divinylbenzene %, 〉=								?????????45			???????????55				?SH/T1485.2
	Diethylbenzene % ,≤	?6.0	?8.0	?12.0	??2.5	??4.0	??6.0							?SH/T1485.2
Naphthalene % ,≤								?1.5	?1.5	?2.0	??1.5	??1.5	??2.0		?SH/T1485.2
	Bromine index gBr/100g, 〉=	?165	?160	?155	??180	??175	??170							?SH/T1485.5
T-butyl catechol %								????0.09～0.11							?SH/T1485.4
	Polymkeric substance % ,≤	????0.005												?SH/T1485.3

DVB45, DVB55 are used in different resins, and DVB45 is mainly used in gel resin, and DVB55 is mainly used in macroporous resin.The grade that above-mentioned standard is worked out is more, can not produce the product that meets customer requirements according to the actual requirements.Below be polymerization and the sulfonation test of carrying out 001 * 7 (strongly acidic styrene type cation exchange resin), partial results is as follows:

Test one:

Lot number	Complete hand over (mmol/g)	Rate of small round spheres (%)	Water content (%)
				1	????4.36	????50	????47.08
2	????1.44	????99	????19.82
				3	????4.48	????86	????46,96
4	????4.46	????96	????46.93
				5	????4.5(H+)	????45	????44.10
6	????4.18	????56	????36.6
				X	????3.90	????72	????40.26

Test two:

Lot number	Complete hand over (mmol/g)	Rate of small round spheres (%)	Water content (%)
				1	????4.6	????49	????49
2	????4.6	????66	????49
				3	????4.6	????56	????51
4	????4.6	????68	????51
				5	????4.5	????69	????49
6	????4.5	????70	????49
				7	????4.6	????67	????50
8	????4.4	????26	????48
				9	????4.4	????68	????48
X	????4.53	????59.89	????49.33

Test three:

Lot number	Complete hand over (mmol/g)	Rate of small round spheres (%)	Water content (%)
				1	????4.5	????92.3	???50.61
2	????4.43	????90	???49.21
				X	????4.465	????91.15	???49.91

Draw from above-mentioned experiment and many experiments: DVB component instability, to the production of resins influence greatly, the fluctuation that produces extreme formula causes many interference, the scrap rate height.The weak point of standard is that it has only noticed the content of DVB, and to, the influence of aligning structure do not consider.Some index even people have been brought into mistaken ideas is few more good more as diethylbenzene content primary standard among the DVB, and the theory and practice proof it be have one reasonably interval.Naphthalene is not participate in polyreaction, should be few more good more, and the content in the standard should reduce again.By a large amount of theories and production practice, whether the ratio of 8 kinds of components is reasonable among the DVB, will produce significant effects to the manufacturing of IER.

The objective of the invention is to determine that ion exchange resin constitutes with the rational formula of divinylbenzene, thereby improve the quality of IER.

Major technique characteristics of the present invention are to determine that the content of diethylbenzene is 2～10%.

Diethylbenzene does not participate in polyreaction, and it is few more good more to be considered as, but by studies confirm that, diethylbenzene plays the effect of telomerizing in copolyreaction, makes the polymer chain solvation.Thereby shorten the mean length of polymer chain.An amount of diethylbenzene can make the IER high resilience, slows down internal stress, and the intensity of resin is strengthened to some extent, and is very helpful to the work-ing life of IER.But measure many, the one, can change make the structure of ion exchange resin with Archon, deviate from original manufacturing route, make synthetic out of hand; The 2nd, make the polymeric chain contraction in length, Archon fragility increases, and mechanical strength of resin descends, and the interlinkage degree changes to some extent.2～10%, a reasonable interval of determining, the preferred content scope is 3～8%.

Another technical characterstic of the present invention is the content that improves divinylbenzene.The minimum content of primary standard DVB is on the low side, and the exchange capacity to IER decreases like this, and other component increases among the DVB simultaneously, to synthetic also unfavorable.It is an indefinite scope (more than or equal to a numerical value) simultaneously, the present invention determines that the content of divinylbenzene improves about 5 percentage points than original, the divinylbenzene that suitable gel resin is used, the content of DVB is 48～52%%, to suitable macroporous resin divinylbenzene, the content of DVB is 58～62%.It no longer is an indefinite scope, and also being has a rational span.

The quality of position and two kinds of isomer of contraposition also produces great effect to the IER quality between divinylbenzene.Because their reactivity ratios in polyreaction are different, their the reasonably combined product that will make is better, as not limited, then can occur unordered and chaotic.To the divinylbenzene that suitable gel resin is used, p-DVB: m-DVB=1: 2～2.3; To suitable macroporous resin divinylbenzene, p-DVB: m-DVB=1: 1.8～2.0.

Naphthalene in the divinylbenzene is no advantage to polyreaction, should strict its existence of control, and the divinylbenzene that the content of naphthalene of the present invention is used suitable gel resin is below 1%, and to suitable macroporous resin divinylbenzene, naphthalene content is below 1.5%.

Triethyl-benzene amount in the divinylbenzene is minimum, below 0.5%.Ethyl styrene is a variable.

Product index of the present invention is as follows:

Project	Index
			Outward appearance	Light yellow transparent liquid
Divinylbenzene %	??50±2	??60±2
			Diethylbenzene %	????2～10
Ethyl styrene %	Variable
			% such as naphthalene≤	??1	????1.5
??TBC?????????％	??0.09～0.11	????0.11～0.13
			Polymkeric substance %≤	??0.0020	????0.0020
Bromine index 〉=	??165	????180

Production technique of the present invention still adopts by diethylbenzene through catalytic dehydrogenation, rectification process.

The existing technology of following summary earlier:

Dehydrogenation reaction: diethylbenzene is under katalysis, carry out dehydrogenation reaction, the condensation in the dehydrogenation condenser of reaction back gas, liquid under first and second condenser condenses flows into water-and-oil separator, furnace oil (dehydrogenation liquid) overflow that separates moisture through water-and-oil separator and subsider is gone into stopper (TBC) and is added cylinder, after adding quantitative stopper, return dehydrogenation liquid vat.

Rectifying: dehydrogenation liquid enters topping still by the middle part after preheating, and under the heat effect of tower still reboiler, low-boiling-point substance, diethylbenzene and a spot of ethyl styrene and divinylbenzene are steamed by cat head, the low tower charging of boiling of conduct after condensation.The divinylbenzene of tower still, ethyl styrene and a small amount of diethylbenzene are adopted into tower still tundish, as the charging of rectifying tower after cooling.

The low tower charging of boiling enters the low tower that boils by the tower middle part after preheating, under the reboiler heat effect, low-boiling-point substance and a small amount of diethylbenzene are steamed by cat head, and cooling back barrelling is dispatched from the factory as byproduct; Adopt into tower still tundish after the diethylbenzene of tower still, ethyl styrene and a small amount of low-boiling-point substance cooling, return the tank field and reclaim big jar of diethylbenzene, recycle as dehydrogenation feed.

By entering rectifying tower in the tower, under the heat effect of reboiler, cat head steams and meets the divinylbenzene that component requires, and imports big jar of finished product DVB after condensation, behind the interpolation TBC, dispatches from the factory after the packing after preheating in the rectifying tower charging of crude distillation column extraction.The height of tower still extraction boil component and a small amount of DVB as byproduct barrelling sell.

The present invention mainly is that the amount of each component changes to some extent, and the major control method is as follows:

(1) control of diethylbenzene content: former technology crude distillation column extraction liquid is as the rectifying tower charging, wherein the content of diethylbenzene has only 2～3% sometimes, can't satisfy requirement of the present invention, if be blended into the raw material diethylbenzene, then can bring impurities in raw materials into, so adopt the diethylbenzene (diethylbenzene 85%) that the low tower still that boils is reclaimed to be blended in the crude distillation column liquid,, can satisfy the requirement of diethylbenzene content as the rectifying tower charging.

(2) between divinylbenzene, the control of para-isomeride ratio: find that through long-term follow temperature of reaction is in the time of 580 ℃, contraposition diethylbenzene reacting phase is to active, and when temperature reached 600 ℃, the formation speed of a position DVB was accelerated relatively.Make suitable scope according to raw material condition.

(3) control of naphthalene content: rectifying tower is used charging in the tower instead, and guarantees the backflow of 50l/h, has improved the separating effect of this tower, makes that naphthalene content is controlled within the index in the finished product.

Advantage of the present invention:

The present invention has determined that the rational formula of divinylbenzene constitutes, and it is too much to have overcome prior art standard middle grade kind, the defective that value is indefinite.The high-grade-goods rate of IER is improved more than 30%, and mill back rate of small round spheres improves more than 10%, and has stablized production, and the fluctuation of extreme formula has reduced loss due to spoiled work in having stopped to produce, and has remarkable economic efficiency and social benefit.Xi-an Electric Power Resin Factory uses original DVB to be used for IER production, and bad when causing the quality product fashion, loss due to spoiled work reached 1,000,000 yuan in 94 years, product of the present invention should be arranged after, stopped waste product, make high-grade-goods rate improve 35%.With divinylbenzene production 001 * 7 of the present invention and 001 * 7-II (macrobead), the result is as follows:

Table one: (001 * 7)

Lot number	Complete hand over (mmol/g)	Rate of small round spheres %	Water content %
				????1	????4.51	????96	?49.50
????2	????4.50	????96	?48.96
				????3	????4.51	????95	?49.47
????4	????4.52	????97	?50.01
				????5	????4.53	????95	?50.11
????6	????4.51	????96	?49.72
				????7	????4.55	????98	?49.96
????8	????4.53	????96	?48.99
				????9	????4.51	????96	?49.06
????10	????4.52	????96	?50.12
				????X	????4.52	??96	?49.59

Table two: (001 * 7-11)

Lot number	Complete hand over (mmol/g)	Rate of small round spheres %	Water content %
				????1	????4.52	????94	?49.07
????2	????4.53	????94	?50.02
				????3	????4.51	????93	?49.79
????4	????4.52	????93	?49.63
				????5	????4.51	????92	?48.89
????6	????4.51	????93	?49.21
				????7	????4.53	????95	?49.42
????8	????4.52	????94	?48.89
				????9	????4.50	????92	?48.78
????10	????4.53	????94	?48.95
				????X	????4.52	????93.4	?49.55

Find out from experimental result, produce more stablely, avoided the fluctuation of extreme formula, mill back rate of small round spheres improves.

Embodiment:

1, feed composition situation:

Diethylbenzene content 90% (P-31,58, m-58.42)

Low boiling mixture content 7%

Triethyl-benzene 3%

2,20 tons of production task: DVB50

3, production process Control essentials summary:

(1) to note controlling well furnace temperature and preheating temperature in the dehydrogenation process operations, temperature of reaction be stablized be controlled at 580 ℃,, the m-DVB content in the dehydrogenation liquid be improved, to reach p-DVB: m-DVB=1: 2～2.3 to accelerate the speed of response of contraposition diethylbenzene.

(2) control the feeding preheating temperature (65～70 ℃) and the reboiler temperature (85～90 ℃) of topping still well, make the crude distillation column sample be controlled at 52% (divinylbenzene content), diethylbenzene content does not need to add diethylbenzene 34% again.

(3) utilize rectifying tower that the impurity such as naphthalene in the thick tower bottoms are sloughed, take away a small amount of divinylbenzene simultaneously, so the divinylbenzene content that cat head steams reduces than crude distillation column liquid, and diethylbenzene content increases.(4) the finished product situation is as follows:

Divinylbenzene content 50%

Diethylbenzene content 5%

Ethyl styrene content 44.2%

Naphthalene etc. 0.8%

Claims (8)

1, the divinylbenzene that is used for ion exchange resin is characterized in that containing 2～10% diethylbenzene.

2, divinylbenzene according to claim 1, the preferred content that is characterised in that diethylbenzene is 3～8%.

3, divinylbenzene according to claim 1, the content that is characterised in that divinylbenzene is 48～52%.

4, divinylbenzene according to claim 3 is characterised in that the mass ratio of a contraposition divinylbenzene and a position divinylbenzene is: 1: 2～2.3.

5,, be characterised in that and contain naphthalene≤1% according to claim 3,4 described divinylbenzenes.

6, divinylbenzene according to claim 1, the content that is characterised in that divinylbenzene is 58～62%.

7, divinylbenzene according to claim 6 is characterised in that the mass ratio of a contraposition divinylbenzene and a position divinylbenzene is: 1: 1.8～2.0.

8,, be characterised in that and contain naphthalene≤1.5% according to claim 6,7 described divinylbenzenes.