CN108034265A

CN108034265A - A kind of preparation method of flame-proof damp-proof type heat stabilizer

Info

Publication number: CN108034265A
Application number: CN201711282695.7A
Authority: CN
Inventors: 管小梅; 杨亚生; 张建初
Original assignee: Changzhou Dijun Metal Component Factory
Current assignee: Changzhou Dijun Metal Component Factory
Priority date: 2017-12-07
Filing date: 2017-12-07
Publication date: 2018-05-15

Abstract

The present invention relates to polyvinyl chloride（PVC）A kind of plastics organic additive preparing technical field, and in particular to preparation method of flame-proof damp-proof type heat stabilizer.The present invention is modified hydrotalcite powder, and it is dispersed in pvc material inside, improve the anti-flammability of heat stabilizer, by hydrotalcite powder and vegetable oil and Yoghourt co-fermentation, so that ester group is grafted to hydrotalcite powder surface under the action of microorganism, make it have waterproof ability, so as to improve the moisture resistance of heat stabilizer, by ethyl cellulose and castor oil, silicone oil and propane diols are prepared into self-control lotion, and base substrate is immersed in lotion, add aluminium hydroxide reaction, amount of heat is absorbed during decomposition, suppress substrate temperature to rise, and form one layer of aqueous vapor starvation in material surface, improve the anti-flammability of heat stabilizer, with broad prospect of application.

Description

A kind of preparation method of flame-proof damp-proof type heat stabilizer

Technical field

The present invention relates to polyvinyl chloride（PVC）Plastics organic additive preparing technical field, and in particular to a kind of fire-retardant anti- The preparation method of tidal stencils heat stabilizer.

Background technology

Polyvinyl chloride（PVC）It is the thermoplasticity line polymer generated by vinyl chloride monomer through Raolical polymerizable, is The big general-purpose plastics in third place in the world, yield are only second to polyethylene（PE）And polypropylene（PP）.Its product has hardness easy-regulating, power Better performances, the advantages that corrosion-resistant, electrical insulating property is good, transparent high and inexpensive are learned, in building, light industry, chemical industry, electronics, boat My god, the field such as automobile, agricultural tool has been widely used.

But existing defects in PVC structures, thermal stability is poor, and thermal degradation easily occurs in PVC process and shows As.Therefore, usual addition heat stabilizer prevents its degraded, promotes plasticizing, the melting of polyvinyl chloride resin, improves melt strength, reduce and add Work temperature.

Heat stabilizer is one of important class in plastic processing additives, and the birth and development of heat stabilizer and polyvinyl chloride resin are same Step, is mainly used in polyvinyl chloride resin processing.Currently used PVC stabilizer has lead salt composite thermal stabilizer, organotin thermostabilization Agent, metal soap thermal stabilizers, rare earth type thermal stabilizing agent, hydrotalcite heat stabilizer etc..Wherein lead salt type thermal stabilizing agent because It is poisonous, there is pollution to be prohibited from using gradually to environment；And although organic tin heat stabilizer effect is good, price, have it is different The shortcomings of taste, also greatly limit its popularization；Rare earth thermal stabilizer is a kind of distinctive PVC heat stabilizer of China, has heat The characteristics of stability is good, nontoxic, environmentally friendly.But it is not high there are early stage heat endurance, initial coloring is poor, it is impossible to individually decides The shortcomings of stabilizer, is, it is necessary to take into full account the cooperative effect of rare earth thermal stabilizer and other heat stabilizers, by compounding preparation height Composite thermal stabilizer is imitated to improve thermostable effect.

Essential auxiliary agent when heat stabilizer is PVC processing, strengthens the further investigation to its performance, develops a kind of height Effect, nontoxic, inexpensive heat stabilizer are to developing PVC processing technology important in inhibiting.

The content of the invention

The technical problems to be solved by the invention：Air is easily absorbed during storage for current common heat stabilizer Middle moisture, and extremely burn at high temperature, it is limited in the defects of being used in pvc material, there is provided a kind of flame-proof damp-proof The preparation method of type heat stabilizer.

In order to solve the above technical problems, the present invention is using technical solution as described below：

A kind of preparation method of flame-proof damp-proof type heat stabilizer, it is characterised in that specifically preparation process is：

（1）Weigh and 100 mesh sieves are crossed after 40~50g hydrotalcites are ground, sieving hydrotalcite powder is collected, by hydrotalcite powder of sieving End, silane resin acceptor kh-550 and odium stearate are mixed, and obtain mixture, mixture is put into mixture quality In the fermentation tank of 8% peanut oil and the Yoghourt of mixture quality 0.8%, it is sealed by fermentation, takes out tunning, and use deionization Water rinses tunning surface, removes remaining zymotic fluid, and is put into baking oven and dries, and cooled to room temperature, is modified Hydrotalcite；

（2）Weigh and 80 mesh sieves are crossed after 30~40g zeolites are ground, collect sieving zeolite powder, sieving zeolite powder is poured into Soaked in beaker with 100~120mL hydrochloric acid, remove impurity, obtain active zeolite；（3）By ethyl cellulose, lemon yellow Aluminum lake and titanium dioxide are mixed, and obtain self-control mixture 1, then by triethyl citrate, castor oil, silicone oil and propane diols It is mixed, obtains Self-made mixture, is poured into by grade mass ratio by mixture 1 is made by oneself in the beaker with Self-made mixture, after It is continuous to be mixed, obtain self-control lotion；

（4）Count in parts by weight, weigh modified hydrotalcite, active zeolite, paraffin and deionized water mixing respectively and be placed in kneading machine Middle mixing, then maleic anhydride, diketone and aluminium hydroxide are added, continue insulation and be kneaded, cooled to room temperature, discharging obtains hot steady Determine base substrate, thermostabilization base substrate is put into self-control lotion and is soaked, natural air drying, grinding discharging, you can flame-proof damp-proof type heat is made Stabilizer.

Step（1）The time that grinds is 10~12min, sieving hydrotalcite powder, silane resin acceptor kh-550 Mass ratio with odium stearate is 3：2：1, mixing time is 6~8min, and fermentation temperature is 35~45 DEG C, and fermentation time is 6~8 My god, drying temperature is 55~65 DEG C, and drying time is 10~12min.

Step（2）Described to grind the time be 6~8min, and the mass fraction of hydrochloric acid is 20%, soaking time for 1~ 3h。

Step（3）The mass ratio of the ethyl cellulose, tartrazine aluminum lake and titanium dioxide is 3：1：1, during stirring Between be 10~12min, triethyl citrate, castor oil, the volume ratio of silicone oil and propane diols are 2：1：1：1, the time is mixed For 16~20min, it is 35~45 DEG C to continue whipping temp, and continuation mixing time is 1~2h.

Step（4）The meter in parts by weight, weighs 20~30 parts of modified hydrotalcites, 16~20 parts of activation boilings respectively Stone, 4~6 parts of paraffin, 8~10 parts of deionized waters, 10~12 parts of maleic anhydrides, 4~6 parts of diketone and 5~7 parts of aluminium hydroxides, are mixed It is 100~120 DEG C to refine temperature, and mixing time is 20~30min, and continuation mixing time is 1~2h, and soaking time is 1~2h.

Compared with other methods, advantageous effects are the present invention：

（1）The present invention carries out hydrotalcite powder surface to be effectively modified by silane resin acceptor kh-550 and odium stearate first, It is set to be dispersed in pvc material inside, enhancing hydrotalcite powder and the compatibility inside pvc material, have Beneficial to hydrotalcite powder when heated, its constitution water laminated sheet hydroxyl and interlayer ion are deviate from the form of water and carbon dioxide, Play the role of reducing burning gases concentration, and the burning of blocking oxygen, so that the anti-flammability of heat stabilizer is improved, and it is released Fire retardant matter is put, during fire-retardant, caloric receptivity is big, advantageously reduces caused high temperature during burning, improves thermostabilization again The anti-flammability of agent, by itself and vegetable oil and Yoghourt co-fermentation, lipophile ester is produced using antimicrobial plant oil decomposition in Yoghourt Base, and cause ester group to be grafted to hydrotalcite powder surface under the self-crosslinking of microorganism, waterproof ability is made it have, so that Improve the moisture resistance of heat stabilizer；

（2）Active zeolite is prepared using zeolite is acidified in the present invention, since active zeolite has certain fire retardancy, Zeolite dehydration of being heated can not only take away partial heat, but also can dilute fuel gas and play fire retardation, so as to improve heat stabilizer Anti-flammability, have zeolite or titanium dioxide coating in the charcoal layer surface of active zeolite, play preferable adiabatic shielding action, into One step improves the anti-flammability of heat stabilizer；

（3）The present invention has two kinds of nonflammable and not soluble in water properties by ethyl cellulose, by itself and castor oil, silicone oil Self-control lotion is prepared with propane diols, thermostabilization base substrate is immersed in self-control lotion, forms the film of one layer of flame-proof damp-proof, So as to improve the anti-flammability and moisture resistance of heat stabilizer, and aluminium hydroxide is added, crystallization is discharged since it is decomposed at high temperature Water, hydroxide largely absorb heat when decomposing, suppress substrate temperature and rise, reduce flame temperature, steamed with caused water Vapour dilutes fuel gas, and forms one layer of aqueous vapor starvation in material surface, reaches flame retardant effect to a certain extent, from And the anti-flammability of heat stabilizer is improved, have broad application prospects.

Embodiment

Weigh after 40~50g hydrotalcites grind 10~12min and cross 100 mesh sieves, sieving hydrotalcite powder is collected, by matter Amount is than being 3：2：6~8min is mixed in sieving hydrotalcite powder, silane resin acceptor kh-550 and odium stearate by 1, is mixed Compound, in the fermentation tank for the Yoghourt that mixture is put into the peanut oil with mixture quality 8% and mixture quality 0.8%, Is sealed by fermentation 6~8 days at being 35~45 DEG C in temperature, taking-up tunning, and with deionized water rinsing tunning surface, goes Except remaining zymotic fluid, and 10~12min of drying in 55~65 DEG C of baking oven is put into, cooled to room temperature, obtains modified water Talcum, weighs after 30~40g zeolites grind 6~8min and crosses 80 mesh sieves, sieving zeolite powder is collected, by the zeolite powder that sieves Pour into the beaker with the hydrochloric acid that 100~120mL mass fractions are 20% and soak 1~3h, remove impurity, obtain activation boiling Stone, is in mass ratio 3：1：10~12min is mixed in ethyl cellulose, tartrazine aluminum lake and titanium dioxide by 1, is obtained certainly Mixture 1 processed, then be 2 by volume：1：1：1 by triethyl citrate, castor oil, silicone oil and mixed with propylene glycol stir 16~ 20min, obtains Self-made mixture, by waiting mass ratio to be poured into mixture 1 is made by oneself in the beaker with Self-made mixture, 35~ Continue 1~2h of mixing at 45 DEG C, obtain self-control lotion, count in parts by weight, weigh respectively 20~30 parts of modified hydrotalcites, 16~20 parts of active zeolites, 4~6 parts of paraffin and 8~10 parts of deionized water mixing are placed in kneading machine, are 100~120 in temperature 20~30min is kneaded at DEG C, then adds 10~12 parts of maleic anhydrides, 4~6 parts of diketone and 5~7 parts of aluminium hydroxides, continues to keep the temperature Be kneaded 1~2h, cooled to room temperature, discharging obtain thermostabilization base substrate, by thermostabilization base substrate be put into self-control lotion in immersion 1~ 2h, natural air drying, grinding discharging, you can flame-proof damp-proof type heat stabilizer is made.

Example 1

Weigh after 40g hydrotalcites grind 10min and cross 100 mesh sieves, collect sieving hydrotalcite powder, be in mass ratio 3：2：1 6min is mixed in sieving hydrotalcite powder, silane resin acceptor kh-550 and odium stearate, mixture is obtained, mixture is put It is close in the case where temperature is 35 DEG C in the fermentation tank for entering the Yoghourt of peanut oil and mixture quality 0.8% with mixture quality 8% Seal ferment 6 days, takes out tunning, and with deionized water rinsing tunning surface, removes remaining zymotic fluid, and be put into 55 DEG C baking oven in dry 10min, cooled to room temperature, obtains modified hydrotalcite, weighs 30g zeolites and grinds mistake after 6min 80 mesh sieves, collect sieving zeolite powder, and the zeolite powder that sieves is poured into the beaker with the hydrochloric acid that 100mL mass fractions are 20% Middle immersion 1h, removes impurity, obtains active zeolite, be in mass ratio 3：1：1 by ethyl cellulose, tartrazine aluminum lake and dioxy Change titanium and 10min is mixed, obtain self-control mixture 1, then be 2 by volume：1：1：1 by triethyl citrate, castor oil, silicon Oil and mixed with propylene glycol stir 16min, obtain Self-made mixture, are mixed by waiting mass ratio to pour into self-control mixture 1 with self-control In the beaker for closing liquid, continue that 1h is mixed at 35 DEG C, obtain self-control lotion, count in parts by weight, weigh 20 parts respectively and change Property hydrotalcite, 16 parts of active zeolites, 4 parts of paraffin and the mixing of 8 parts of deionized waters be placed in kneading machine, mixed at being 100 DEG C in temperature 20min is refined, then adds 10 parts of maleic anhydrides, 4 parts of diketone and 5 parts of aluminium hydroxides, continues insulation and is kneaded 1h, naturally cool to room Temperature, discharging obtain thermostabilization base substrate, and thermostabilization base substrate is put into self-control lotion and soaks 1h, natural air drying, grinding discharging, you can Flame-proof damp-proof type heat stabilizer is made.

Example 2

Weigh after 45g hydrotalcites grind 11min and cross 100 mesh sieves, collect sieving hydrotalcite powder, be in mass ratio 3：2：1 7min is mixed in sieving hydrotalcite powder, silane resin acceptor kh-550 and odium stearate, mixture is obtained, mixture is put It is close in the case where temperature is 40 DEG C in the fermentation tank for entering the Yoghourt of peanut oil and mixture quality 0.8% with mixture quality 8% Seal ferment 7 days, takes out tunning, and with deionized water rinsing tunning surface, removes remaining zymotic fluid, and be put into 60 DEG C baking oven in dry 11min, cooled to room temperature, obtains modified hydrotalcite, weighs 35g zeolites and grinds mistake after 7min 80 mesh sieves, collect sieving zeolite powder, and the zeolite powder that sieves is poured into the beaker with the hydrochloric acid that 110mL mass fractions are 20% Middle immersion 2h, removes impurity, obtains active zeolite, be in mass ratio 3：1：1 by ethyl cellulose, tartrazine aluminum lake and dioxy Change titanium and 11min is mixed, obtain self-control mixture 1, then be 2 by volume：1：1：1 by triethyl citrate, castor oil, silicon Oil and mixed with propylene glycol stir 18min, obtain Self-made mixture, are mixed by waiting mass ratio to pour into self-control mixture 1 with self-control In the beaker for closing liquid, continue that 1.5h is mixed at 40 DEG C, obtain self-control lotion, count in parts by weight, weigh 25 parts respectively Modified hydrotalcite, 18 parts of active zeolites, 5 parts of paraffin and 9 parts of deionized water mixing are placed in kneading machine, in the case where temperature is 110 DEG C 25min is kneaded, then adds 11 parts of maleic anhydrides, 5 parts of diketone and 6 parts of aluminium hydroxides, continues insulation and is kneaded 1.5h, naturally cool to Room temperature, discharging obtain thermostabilization base substrate, and thermostabilization base substrate is put into self-control lotion and soaks 1.5h, natural air drying, grinding discharging, It can be prepared by flame-proof damp-proof type heat stabilizer.

Example 3

Weigh after 50g hydrotalcites grind 12min and cross 100 mesh sieves, collect sieving hydrotalcite powder, be in mass ratio 3：2：1 8min is mixed in sieving hydrotalcite powder, silane resin acceptor kh-550 and odium stearate, mixture is obtained, mixture is put It is close in the case where temperature is 45 DEG C in the fermentation tank for entering the Yoghourt of peanut oil and mixture quality 0.8% with mixture quality 8% Seal ferment 8 days, takes out tunning, and with deionized water rinsing tunning surface, removes remaining zymotic fluid, and be put into 65 DEG C baking oven in dry 12min, cooled to room temperature, obtains modified hydrotalcite, weighs 40g zeolites and grinds mistake after 8min 80 mesh sieves, collect sieving zeolite powder, and the zeolite powder that sieves is poured into the beaker with the hydrochloric acid that 120mL mass fractions are 20% Middle immersion 3h, removes impurity, obtains active zeolite, be in mass ratio 3：1：1 by ethyl cellulose, tartrazine aluminum lake and dioxy Change titanium and 12min is mixed, obtain self-control mixture 1, then be 2 by volume：1：1：1 by triethyl citrate, castor oil, silicon Oil and mixed with propylene glycol stir 20min, obtain Self-made mixture, are mixed by waiting mass ratio to pour into self-control mixture 1 with self-control In the beaker for closing liquid, continue that 2h is mixed at 45 DEG C, obtain self-control lotion, count in parts by weight, weigh 30 parts respectively and change Property hydrotalcite, 20 parts of active zeolites, 6 parts of paraffin and the mixing of 10 parts of deionized waters be placed in kneading machine, mixed at being 120 DEG C in temperature 30min is refined, then adds 12 parts of maleic anhydrides, 6 parts of diketone and 7 parts of aluminium hydroxides, continues insulation and is kneaded 2h, naturally cool to room Temperature, discharging obtain thermostabilization base substrate, and thermostabilization base substrate is put into self-control lotion and soaks 2h, natural air drying, grinding discharging, you can Flame-proof damp-proof type heat stabilizer is made.

The heat stabilizer that comparative example is produced with Wuxi City company is as a comparison case to flame-proof damp-proof produced by the present invention Heat stabilizer in type heat stabilizer and comparative example is detected, and testing result is as shown in table 1：1st, long-term thermal stability is tested：

Using oven heat method, performed according to GB/T9349-2002 standards.Present example 1~3 will be with the addition of and comparative example heat is steady Determine the PVC pieces not of the same race obtained by agent and be cut into the square that the length of side is 15mm respectively, Oven test is done at 180 DEG C. By the quality of the change characterization heat stabilizer static heat stability of print color, its result corresponds to long-term thermal stability.

1st, combustibility test is detected by the regulation of GB/T2408-2008.

2nd, humidity resistance is tested：

It will with the addition of present example 1~3 and the PVC not of the same race obtained by comparative example heat stabilizer be respectively cut into the length of side and be The square of 50mm × 50mm × 50mm, place it in 70 DEG C of water 72 it is small when, test weight increase ratio, observes test block surface Situation.

Table 1

Test event	Example 1	Example 2	Example 3	Comparative example
					Long-term thermal stability（120min colors）	It is pale yellow	It is pale yellow	It is pale yellow	White
Oxygen index (OI)	47	47	48	39
					Weight increases ratio（%）	0.050	0.042	0.035	0.650

According to data in table 1, with the addition of flame-proof damp-proof type heat stabilizer produced by the present invention PVC be respectively provided with it is good anti- Damp performance and heat endurance, and there is certain fire retardation, there is wide prospect of the application.

Claims

1. a kind of preparation method of flame-proof damp-proof type heat stabilizer, it is characterised in that specifically preparation process is：

（2）Weigh and 80 mesh sieves are crossed after 30~40g zeolites are ground, collect sieving zeolite powder, sieving zeolite powder is poured into Soaked in beaker with 100~120mL hydrochloric acid, remove impurity, obtain active zeolite；

（3）Ethyl cellulose, tartrazine aluminum lake and titanium dioxide are mixed, obtain self-control mixture 1, then by citric acid Triethyl, castor oil, silicone oil and mixed with propylene glycol stirring, obtain Self-made mixture, are poured into by mass ratio is waited by mixture 1 is made by oneself In beaker with Self-made mixture, continue to be mixed, obtain self-control lotion；

A kind of 2. preparation method of flame-proof damp-proof type heat stabilizer according to claim 1, it is characterised in that：Step（1） The time that grinds is 10~12min, the quality of sieving hydrotalcite powder, silane resin acceptor kh-550 and odium stearate Than for 3：2：1, mixing time is 6~8min, and fermentation temperature is 35~45 DEG C, and fermentation time is 6~8 days, drying temperature 55 ~65 DEG C, drying time is 10~12min.

A kind of 3. preparation method of flame-proof damp-proof type heat stabilizer according to claim 1, it is characterised in that：Step（2） The time that grinds is 6~8min, and the mass fraction of hydrochloric acid is 20%, and soaking time is 1~3h.

A kind of 4. preparation method of flame-proof damp-proof type heat stabilizer according to claim 1, it is characterised in that：Step（3） The mass ratio of the ethyl cellulose, tartrazine aluminum lake and titanium dioxide is 3：1：1, mixing time is 10~12min, lemon Lemon triethylenetetraminehexaacetic acid ester, castor oil, the volume ratio of silicone oil and propane diols are 2：1：1：1, the mixing time is 16~20min, is continued Whipping temp is 35~45 DEG C, and continuation mixing time is 1~2h.

A kind of 5. preparation method of flame-proof damp-proof type heat stabilizer according to claim 1, it is characterised in that：Step（4） The meter in parts by weight, weigh respectively 20~30 parts of modified hydrotalcites, 16~20 parts of active zeolites, 4~6 parts of paraffin, 8~ 10 parts of deionized waters, 10~12 parts of maleic anhydrides, 4~6 parts of diketone and 5~7 parts of aluminium hydroxides, melting temperature are 100~120 DEG C, mixing time is 20~30min, and continuation mixing time is 1~2h, and soaking time is 1~2h.