CN105295248A - Hydrotalcite-dimer acid lanthanum composite environmental protection stabilizer for PVC, and preparation method thereof - Google Patents

Abstract

The present invention provides a hydrotalcite-dimer acid lanthanum composite environmental protection stabilizer for PVC, wherein the hydrotalcite-dimer acid lanthanum composite environmental protection stabilizer is prepared from the following raw materials by weight: 20-30 parts of modified magnesium aluminum hydrotalcite, 10-12 parts of dibutyl tin oxide, 6-9 parts of dimer acid lanthanum, 1-3 parts of triphenyl phosphite, 3-6 parts of zinc stearate, 2-4 parts of epoxidized soybean oil, 5-6 parts of beta-diketone, 2-4 parts of 2,2'-thiobis(4-tert-octylphenoloxy)nickel, 12-15 parts of triethyl acetyl citrate, 1-2 parts of montan wax, and 10-15 parts of attapulgite. According to the present invention, the PVC stabilizer has characteristics of good thermal stability, good processing performance, environmental protection, no toxicity, low cost, good plasticity and balance torque reducing during the PVC processing process, and low cost.

Description

A kind of PVC hydrotalcite dimeracid lanthanum composite environmental-friendly stablizer and preparation method thereof

Technical field

The present invention relates to PVC auxiliary agent field, be specifically related to a kind of PVC hydrotalcite dimeracid lanthanum composite environmental-friendly stablizer and preparation method thereof.

Background technology

PVC is generally applied in the fields such as chemical industry, material, machinery, agricultural, daily necessities with its superior physicals and cheap cost, is especially widely used at plastic applications, is called as one of five large general-purpose plastics.But PVC has a very important defect, be exactly when hot-work, easily decompose and produce HCl gas, the degraded that autocatalysis causes PVC violent, and affect the various performances of PVC product, as made the variable color of PVC product or reducing its mechanical property etc.In order to overcome this defect of PVC, mainly in the hot procedure of PVC, add appropriate stablizer at present.

The thermo-stabilizer of present widespread commercialization only has lead salts, organic tin and metal soap.And lead salt stabilizer exists toxicity and cause series of environmental problems, therefore lead salt composite thermal stabilizer is complied with trend and is born, although the usage quantity of lead salt decreases, but still exists and poisons, and eliminating of the plumbous thermo-stabilizer of cadmium has been the certainty of history.And although organotin thermostability is high, pollution hazard is little, expensive, and cost is high, and has peculiar smell, does not meet the production national conditions of China's present stage, makes it develop and be in constrained state.Metal soap thermal stabilizers effect limited capacity.

Along with the enhancing of people to environmental consciousness and the requirement to environment more and more higher, the Non-toxic of PVC stablizer is the certainty of following stablizer development.Rare earth thermal stabilizer has good thermal stability, but early stage thermostability is not high, initial coloring is poor, main stabilizer can not be done separately, it is made to apply and popularization is subject to a definite limitation, the application of single rare earth thermo-stabilizer is often difficult to the requirement meeting PVC processing and application performance, and Composite, multifunctional type rare earth thermal stabilizer have been the trend of development.Rare earth thermal stabilizer and other auxiliary agents with the use of time, can produce synergistic effect, effectively can improve thermostable effect, the over-all properties of its double matching type heat stabilizer is often better than traditional lead salt and metal soap stablizer, in some applications, rare earth composite stabilizer partly or entirely can replace organotin.China's rare earth resources enriches, and accounts for 23% of world saving.Therefore the rare earth resources making full use of China develops the distinctive performance efficiency of a kind of China, nontoxic, the low price rare earth complex heat stabilizer that meets the current production national conditions of China, realize the efficiency utilization of China's rare earth resources, have very important significance, developing PVC is efficient, nontoxic composite heat stabilizer has become must.

Summary of the invention

The invention discloses a kind of PVC hydrotalcite dimeracid lanthanum composite environmental-friendly stablizer and preparation method thereof.PVC stabilizer of the present invention has good thermostability and processing characteristics, and environment-protecting asepsis, with low cost, and in the course of processing of PVC, soffening is good and can reduce balancing torque, and light transmission is good, and cost is low.

The technical solution used in the present invention is as follows for achieving the above object:

A kind of PVC hydrotalcite dimeracid lanthanum composite environmental-friendly stablizer, it is characterized in that: it is prepared by the component raw material of following weight part and obtains: modification magnesium aluminum-hydrotalcite 20-30, Dibutyltin oxide 10-12, dimeracid lanthanum 6-9, triphenyl phosphite 1-3, Zinic stearas 3-6, epoxy soybean oil 2-4, beta-diketon 5-6,2,2'-thiobiss (4-tertiary octyl phenol oxygen base) nickel 2-4, acetyl triethyl citrate 12-15, montanin wax 1-2, attapulgite 10-15.

The preparation method of described PVC hydrotalcite dimeracid lanthanum composite environmental-friendly stablizer, is characterized in that, comprise the following steps:

(1) preparation of modified hydrotalcite:

A, get a certain amount of Mg (NO3) 26H2O and Al (NO3) 39H2O and be added to the water and be made into the salts solution that total mol concentration is 0.6mol/L, get a certain amount of NaOH and Na2CO3 and add in deionized water that to be made into total mol concentration be 0.6mol/L alkaline solution, by alkaline solution with 1-2 drip/s speed drops in salts solution, N ₂the lower violent stirring of protection, constant temperature 38-42 DEG C, pH value remains between 9.5-10, at stirring 1-1.5h after dropwising, after 75 DEG C of crystallization 8h suction filtrations, washing is to neutral, will precipitate 45-50 DEG C of oven dry, obtain Mg/Al hydrotalcite, wherein the mol ratio of Mg (NO3) 26H2O and Al (NO3) 39H2O is the mol ratio 2:1 of 2:3, NaOH and Na2CO3, the volume ratio 1-1.2:1 of alkaline solution and salts solution during dropping;

B, toxilic acid and citric acid take according to the ratio that mol ratio is 1:1-2 and are a certain amount ofly dissolved in analytical pure ethylene glycol, after abundant mixing, add the Mg/Al hydrotalcite that step (1) is obtained, under 85-88 DEG C of constant temperature, stir 9-10h, by product suction filtration, washing, 75 DEG C of freeze-day with constant temperature 20-22h, i.e. obtained modification magnesium aluminum-hydrotalcite, the quality of described toxilic acid and the quality both citric acid and the volume ratio 0.01-0.02g/mL with ethylene glycol, Mg/Al hydrotalcite and toxilic acid and citric acid and ratio be 1:1-1.5;

(2) by formula rate, modification magnesium aluminum-hydrotalcite obtained for step (1), Dibutyltin oxide, dimeracid lanthanum, triphenyl phosphite, Zinic stearas are placed in high energy vibration equipment with the abundant vibration 45-50 minute of the rotating speed of 650-700 rev/min, vibration temperature 50-60 DEG C, obtains mixture A;

(3) add in stirring tank by acetyl triethyl citrate, be slowly warming up to 65-68 DEG C, add all the other components in the obtained mixture A of step (2) and formula, keep homo(io)thermism, fully stir 1.5-2.0 hour, cooling obtains one package stabilizer.

beneficial effect

The application is by modified hydrotalcite, Dibutyltin oxide, dimeracid lanthanum, the one package stabilizer that triphenyl phosphite and other additive compound obtain, there is between raw material fine synergistic stability effect, traditional hydrotalcite can absorb the HCl gas that PVC degraded is deviate from, play heat-staple effect, but primary stability is bad, the application adopts toxilic acid and citric acid to carry out modification to hydrotalcite LDH, the modified primary stability of hydrotalcite LDH to PVC improves a lot, modified hydrotalcite LDH is carrying out composite with organotin and rare earth and other auxiliary addition agent agent, obtain the one package stabilizer of the application, it has synergistic stability effect to PVC, while improving stability, reduce goods cost, the ligand complex ability that rare earth is stronger, with the unstable chlorine effect in PVC, thus heat stabilization is played to PVC, rare earth has initial stage anti-zinc and burns ability and long-term thermal stability, good effect is had to the resistance toheat and mechanical property that improve PVC plastic, have nontoxic, radioprotective, efficiently, environmental protection good characteristic, and cost is low.

In a word, PVC stabilizer of the present invention has good thermostability and processing characteristics, and environment-protecting asepsis, with low cost, and in the course of processing of PVC, soffening is good and can reduce balancing torque, and cost is low.

Embodiment

A kind of PVC hydrotalcite dimeracid lanthanum composite environmental-friendly stablizer, it is prepared by the component raw material of following weight (kg) and obtains: modification magnesium aluminum-hydrotalcite 25, Dibutyltin oxide 11, dimeracid lanthanum 8, triphenyl phosphite 2, Zinic stearas 5, epoxy soybean oil 3, beta-diketon 6,2,2'-thiobis (4-tertiary octyl phenol oxygen base) nickel 3, acetyl triethyl citrate 13, montanin wax 2, attapulgite 14

Preparation method is as follows:

(1) preparation of modified hydrotalcite:

A, get a certain amount of Mg (NO3) 26H2O and Al (NO3) 39H2O and be added to the water and be made into the salts solution that total mol concentration is 0.6mol/L, get a certain amount of NaOH and Na2CO3 and add in deionized water that to be made into total mol concentration be 0.6mol/L alkaline solution, by alkaline solution with 1-2 drip/s speed drops in salts solution, N ₂the lower violent stirring of protection, constant temperature 38-42 DEG C, pH value remains between 9.5-10, at stirring 1-1.5h after dropwising, after 75 DEG C of crystallization 8h suction filtrations, washing is to neutral, will precipitate 45-50 DEG C of oven dry, obtain Mg/Al hydrotalcite, wherein the mol ratio of Mg (NO3) 26H2O and Al (NO3) 39H2O is the mol ratio 2:1 of 2:3, NaOH and Na2CO3, the volume ratio 1-1.2:1 of alkaline solution and salts solution during dropping;

B, toxilic acid and citric acid take according to the ratio that mol ratio is 1:1-2 and are a certain amount ofly dissolved in analytical pure ethylene glycol, after abundant mixing, add the Mg/Al hydrotalcite that step (1) is obtained, under 85-88 DEG C of constant temperature, stir 9-10h, by product suction filtration, washing, 75 DEG C of freeze-day with constant temperature 20-22h, i.e. obtained modification magnesium aluminum-hydrotalcite, the quality of described toxilic acid and the quality both citric acid and the volume ratio 0.01-0.02g/mL with ethylene glycol, Mg/Al hydrotalcite and toxilic acid and citric acid and ratio be 1:1-1.5;

(2) by formula rate, modification magnesium aluminum-hydrotalcite obtained for step (1), Dibutyltin oxide, dimeracid lanthanum, triphenyl phosphite, Zinic stearas are placed in high energy vibration equipment with the abundant vibration 45-50 minute of the rotating speed of 650-700 rev/min, vibration temperature 50-60 DEG C, obtains mixture A;

(3) add in stirring tank by acetyl triethyl citrate, be slowly warming up to 65-68 DEG C, add all the other components in the obtained mixture A of step (2) and formula, keep homo(io)thermism, fully stir 1.5-2.0 hour, cooling obtains one package stabilizer.

The mensuration of thermal stability

1, static heat stability measures:

By 3.5:100 ratio of quality and the number of copies, the composite thermal stabilizer produce the present embodiment and Ga/Zn one package stabilizer add in PVC respectively, and adopt congo-red test paper method to determine static heat stability, result is as follows:

Static heat steady time of Ga/Zn one package stabilizer is 60min, composite thermal stabilizer static heat steady time that the present embodiment is produced is 131min, can find out that composite thermal stabilizer static heat stability that the present embodiment is produced obviously is better than the static heat stability of Ga/Zn one package stabilizer.

2, dynamic thermal stability measures:

Add the condition of 3.5 parts of thermo-stabilizers in 100 parts of PVC under, measure Ga/Zn one package stabilizer respectively, the dynamic thermal stability energy of the composite thermal stabilizer that the present embodiment is produced, result is: the heat-stable time of Ga/Zn one package stabilizer is 35.6min, plasticizing torque and balancing moment are 52Nm and 31.0Nm, the heat-stable time of the composite thermal stabilizer that the present embodiment is produced is 49min, plasticizing torque and balance torque drop are 43.2Nm and 23.4Nm, compared with Ga/Zn one package stabilizer, steady time obviously extends, plasticizing torque and balancing moment obviously decline, can find out that stablizer of the present invention more effectively can improve PVC dynamic thermal stability energy, reduce power consumption of polymer processing.

Claims (2)

1. a PVC hydrotalcite dimeracid lanthanum composite environmental-friendly stablizer, it is characterized in that: it is prepared by the component raw material of following weight part and obtains: modification magnesium aluminum-hydrotalcite 20-30, Dibutyltin oxide 10-12, dimeracid lanthanum 6-9, triphenyl phosphite 1-3, Zinic stearas 3-6, epoxy soybean oil 2-4, beta-diketon 5-6,2,2'-thiobiss (4-tertiary octyl phenol oxygen base) nickel 2-4, acetyl triethyl citrate 12-15, montanin wax 1-2, attapulgite 10-15.

2. the preparation method of PVC hydrotalcite dimeracid lanthanum composite environmental-friendly stablizer according to claim 1, is characterized in that, comprise the following steps:

(1) preparation of modified hydrotalcite:

A, get a certain amount of Mg (NO3) 26H2O and Al (NO3) 39H2O and be added to the water and be made into the salts solution that total mol concentration is 0.6mol/L, get a certain amount of NaOH and Na2CO3 and add in deionized water that to be made into total mol concentration be 0.6mol/L alkaline solution, by alkaline solution with 1-2 drip/s speed drops in salts solution, N ₂the lower violent stirring of protection, constant temperature 38-42 DEG C, pH value remains between 9.5-10, at stirring 1-1.5h after dropwising, after 75 DEG C of crystallization 8h suction filtrations, washing is to neutral, will precipitate 45-50 DEG C of oven dry, obtain Mg/Al hydrotalcite, wherein the mol ratio of Mg (NO3) 26H2O and Al (NO3) 39H2O is the mol ratio 2:1 of 2:3, NaOH and Na2CO3, the volume ratio 1-1.2:1 of alkaline solution and salts solution during dropping;

B, toxilic acid and citric acid take according to the ratio that mol ratio is 1:1-2 and are a certain amount ofly dissolved in analytical pure ethylene glycol, after abundant mixing, add the Mg/Al hydrotalcite that step (1) is obtained, under 85-88 DEG C of constant temperature, stir 9-10h, by product suction filtration, washing, 75 DEG C of freeze-day with constant temperature 20-22h, i.e. obtained modification magnesium aluminum-hydrotalcite, the quality of described toxilic acid and the quality both citric acid and the volume ratio 0.01-0.02g/mL with ethylene glycol, Mg/Al hydrotalcite and toxilic acid and citric acid and ratio be 1:1-1.5;

(2) by formula rate, modification magnesium aluminum-hydrotalcite obtained for step (1), Dibutyltin oxide, dimeracid lanthanum, triphenyl phosphite, Zinic stearas are placed in high energy vibration equipment with the abundant vibration 45-50 minute of the rotating speed of 650-700 rev/min, vibration temperature 50-60 DEG C, obtains mixture A;

(3) add in stirring tank by acetyl triethyl citrate, be slowly warming up to 65-68 DEG C, add all the other components in the obtained mixture A of step (2) and formula, keep homo(io)thermism, fully stir 1.5-2.0 hour, cooling obtains one package stabilizer.